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What are the oldest known writings that state that Mary was without sin?

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Why did you remove the immaculate-conception tag? That is what you are asking about, not the virginity of Mary! Immaculate conception on Wikipedia –  curiousdannii Jun 21 '14 at 2:32
From your link: "The doctrine of the immaculate conception of Mary concerns her own conception in her mother's womb, not Mary's conception of Jesus (the virgin birth of Jesus)"- I've never heard that, sorry. I've never heard "immaculate conception" refer to any conception other than Christ's, but I'm not Catholic. The Immaculate Conception tag was indeed correct. Apologies. –  Andrew Jun 21 '14 at 3:17
No worries! The name is a bit confusing (because even if she was born to sin she could still have chosen to sin later), but it is what it is. –  curiousdannii Jun 21 '14 at 3:53
It didn't become dogma in the RCC until Vatican I in the late 1800s, but the concept was believed by individual Catholics before then of course. –  david brainerd Jun 22 '14 at 22:53

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The earliest Christian writings outside the bible are from what are called the Church Fathers, from around the middle of the second century onwards for a few hundred years.

On the Immaculate Conception explicitly, the earliest would appear to be Hippolytus and Origen:

He [Jesus] was the ark formed of incorruptible wood. For by this is signified that His tabernacle [Mary] was exempt from defilement and corruption (Hippolytus, Orat. In Illud, Dominus pascit me, in Gallandi, Bibl. Patrum, II, 496 ante [A.D. 235]).

This Virgin Mother of the Only-begotten of God is called Mary, worthy of God, immaculate of the immaculate, one of the one (Origen, Homily 1 [A.D. 244]).

Earlier writers hint at the doctrine, by comparing Mary to Eve, who was created without the stain of sin:

[Jesus] became man by the Virgin so that the course that was taken by disobedience in the beginning through the agency of the serpent might be also the very course by which it would be put down. Eve, a virgin and undefiled, conceived the word of the serpent and bore disobedience and death. But the Virgin Mary received faith and joy when the angel Gabriel announced to her the glad tidings that the Spirit of the Lord would come upon her and the power of the Most High would overshadow her, for which reason the Holy One being born of her is the Son of God. And she replied, "Be it done unto me according to your word" (Luke 1:38) (Justin Martyr, Dialogue with Trypho 100 [A.D. 155]).

Consequently, then, Mary the Virgin is found to be obedient, saying, "Behold, O Lord, your handmaid; be it done to me according to your word." Eve . . . who was then still a virgin although she had Adam for a husband — for in paradise they were both naked but were not ashamed; for, having been created only a short time, they had no understanding of the procreation of children . . . having become disobedient [sin], was made the cause of death for herself and for the whole human race; so also Mary, betrothed to a man but nevertheless still a virgin, being obedient [no sin], was made the cause of salvation for herself and for the whole human race. . . . Thus, the knot of Eve's disobedience was loosed by the obedience of Mary. What the virgin Eve had bound in unbelief, the Virgin Mary loosed through faith (Iranaeus, Against Heresies 3:22:24 [A.D. 189]).

There are further, later comments where I found those but those are the earliest cited. These four are the earliest of the Fathers.

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Luke 1:28:

And the angel being come in, said unto her: Hail, full of grace [κεχαριτωμένη], the Lord is with thee: blessed art thou among women.

To be full of grace to such an extent as to conceive the 2nd Person of the Holy Trinity is incompatible with sinning.

From the Haydock Commentary on Luke 1:28:

Hail, full of grace: [5] by the greatest share of divine graces granted to any creature. This translation, approved by the ancient Fathers, agrees with the ancient Syriac and Arabic versions. There was no need therefore to change it into gracious, with Erasmus; into freely beloved, with Beza; into highly favoured, with the Prot. translators. For if seven deacons (Acts vi. 3.) are said to be full of the Holy Ghost, as it is again said of S. Stephen, (Acts vii. 55.) and also of the same S. Stephen, (Acts vi. v. 8.) that he was full of grace, (as the learned Dr. Wells translates it in his amendments made to the Prot. translation) why should any one be offended at this salutation given to the blessed mother of God; who would not have been raised to this highest dignity, had not her s\oul been first prepared for it by the greatest share of divine graces? — The Lord is with thee, by his interior graces; and now, at this moment, is about to confer upon thee the highest of all dignities, by making thee truly the mother of God. Wi. — The Catholic Church makes frequent use of these words which were brought by the archangel from heaven, as well to honour Jesus Christ and his virgin Mother, as because they were the first glad tidings of Christ's incarnation, and man's salvation; and are the very abridgment and sum of the whole gospel. In the Greek Church, they are used daily in the Mass. See the Liturgy of S. James, and that of S. Chrysos.

Pope Pius IX gives in his dogmatic definition on the Immaculate Conception, Ineffabilis Deus (1854), many reasons for Mary's sinlessness. Here's what he says about Luke 1:28 and Luke 1:42:

When the Fathers and writers of the Church meditated on the fact that the most Blessed Virgin was, in the name and by order of God himself, proclaimed full of grace [Cf. Lk 1:28.] by the Angel Gabriel when he announced her most sublime dignity of Mother of God, they thought that this singular and solemn salutation, never heard before, showed that the Mother of God is the seat of all divine graces and is adorned with all gifts of the Holy Spirit. To them Mary is an almost infinite treasury, an inexhaustible abyss of these gifts, to such an extent that she was never subject to the curse and was, together with her Son, the only partaker of perpetual benediction. Hence she was worthy to hear Elizabeth, inspired by the Holy Spirit, exclaim: "Blessed are you among women, and blessed is the fruit of your womb." [Ibid., 42. ]

He also says:

As if these splendid eulogies and tributes were not sufficient, the Fathers proclaimed with particular and definite statements that when one treats of sin, the holy Virgin Mary is not even to be mentioned; for to her more grace was given than was necessary to conquer sin completely. [Cf. St. Augustine: De Natura et Gratia, c. 36. ] They also declared that the most glorious Virgin was Reparatrix of the first parents, the giver of life to posterity; that she was chosen before the ages, prepared for himself by the Most High, foretold by God when he said to the serpent, "I will put enmities between you and the woman." [Gn 3:15]—unmistakable evidence that she was crushed the poisonous head of the serpent. And hence they affirmed that the Blessed Virgin was, through grace, entirely free from every stain of sin, and from all corruption of body, soul and mind; that she was always united with God and joined to him by an eternal covenant; that she was never in darkness but always in light; and that, therefore, she was entirely a fit habitation for Christ, not because of the state of her body, but because of her original grace.

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How old is the Haydock commentary? –  curiousdannii Jun 23 '14 at 7:08
How do you account for Acts 6:8 then? "And Stephen, full of grace and power, was doing great wonders and signs among the people." Was Stephen sinless too? –  curiousdannii Jun 23 '14 at 7:09
@curiousdannii: Rev. George Leo Haydock (1774-1849). The version I quote from was published in 1859 as Haydock's Catholic Family Bible and Commentary (printed by Edward Dunigan and Brother, New York, New York). –  Geremia Jun 23 '14 at 14:35
@curiousdannii: I think it's safe to say St. Stephen committed no sin at least during the time immediately leading up to and including his martyrdom. Plus, Luke 1:28 also says Mary was (2) with the Lord and (3) blessed. –  Geremia Jun 23 '14 at 14:51
If it is taught by the Church, it has to be from Apostolic times, and the Gospel passage you provide is direct link to this period. –  FMS Aug 28 '14 at 3:58

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