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It is my understanding that the Eastern Orthodox can get married a second time after a separation when their first wife is still living. It is also my understanding that Catholics do not permit this in the Catholic Church. I also believe Catholics recognize Orthodox first marriages as both valid marriages and valid sacraments.

Assuming all of the foregoing is accurate, how do Catholics view Eastern Orthodox second marriages? Valid as both a marriage and a sacrament? Invalid for both? Some other thing? For example, if that couple wanted to convert to Catholicism, would the Church accept them as married?

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Catholic Church canon law considers marriages valid until proven otherwise:

Can. 1060 Marriage possesses the favor of law; therefore, in a case of doubt, the validity of a marriage must be upheld until the contrary is proven.

As canonist Ed Peters says, addressing a complex scenario similar to JoshuaD's here involving conversion to Catholicism (Question 40 of his Annulments and the Catholic Church: Straight Answers to Tough Questions):

you have no power to impugn the former marriage of your current spouse that is preventing your entry into the [Catholic] Church (1983 CIC 1674).

The nullity of the initial marriage in JoshuaD's scenario here must be established:

Can. 1085 §1. A person bound by the bond of a prior marriage, even if it was not consummated, invalidly attempts marriage.

§2. Even if the prior marriage is invalid or dissolved for any reason, it is not on that account permitted to contract another before the nullity or dissolution of the prior marriage is [or must be] established legitimately and certainly.

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In the case of Orthodox marriages, the Catholic Church takes a more positive attitude than merely considering the marriage "valid unless proven otherwise," as suggested by @Geremia's answer. It accepts all Orthodox sacraments as spiritually efficacious, so the marriage is not only valid but is blessed by God.

According to the RCC's decree on ecumenism:

These {Eastern} Churches, although separated from us, possess true sacraments, above all by apostolic succession, the priesthood and the Eucharist, whereby they are linked with us in closest intimacy.

Indeed, in some cases the Catholic Church even allows the validity of marriages between an Orthodox Christian and a Catholic if it is properly administered by an Orthodox priest.

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  • "the Catholic Church even allows the validity of marriages between an Orthodox Christian and a Catholic" Mixed marriages are forbidden unless one obtains a special dispensation from the local bishop. Canonical form must be observed in marriage ceremonies.
    – Geremia
    Nov 4, 2023 at 22:39
  • The statement that you challenged is based on this article, which does not allow copy/pasting. It says that marriages between Catholics and Orthodox without a dispensation are considered "valid" but not "licit" under canon law. Nov 5, 2023 at 0:02
  • Also note that there are exceptions if for example there is no bishop available to give a dispensation. The Church "envisages some exceptional cases in which, whether by law or by dispensation, Catholics may enter into a sacramental marriage in the absence of a bishop, priest or deacon." I understand this to mean that in these cases a lawful inter-marriage (for instance conducted by an Orthodox priest in a small town in Russia) may be accepted as sacramental without a dispensation. usccb.org/committees/ecumenical-interreligious-affairs/… – Nov 5, 2023 at 0:06
  • I have added "in some cases" to my answer to make it clearer. Nov 5, 2023 at 0:09
  • Because the Catholic Church "accepts all Orthodox sacraments as spiritually efficacious", She will accept the initial first marriage as valid and sacramental. Therefore, She will treat it as She treats marriages between Catholics --- which is to say, the second marriage will be considered invalid, unless the first one is determined to be null.
    – ltcomdata
    Nov 5, 2023 at 18:19

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