According to the Catholic Encyclopedia, the Devil's Advocate (Advocatus Diaboli) was:
[a] popular title given to one of the most important officers of the Sacred Congregation of Rites, established in 1587, by Sixtus V, to deal juridically with processes of beatification and canonization.
Yet, toward the end, it says:
The first formal mention of such an officer is found in the canonization of St. Lawrence Justinian under Leo X (1513-21).
I am struggling to find who was the first person to hold such title. Unfortunately, the above text does not provide a reference to where such first formal mention is to be found. I have searched in texts related to the life of Leo X (here and here) without success. I have not found a compilation of the life of St. Lawrence either (which might mention something about his canonisation).
Moving forward, I decided to look for any mention of such person in the life of Sixtus V (compilations also available in www.archive.org), also without success. According to this book, the first saint canonised by Sixtus V (which might have used the services of an Advocatus Diaboli) was Didacus of Alcala. A book about the life of this saint (available here) does not mention much about it, except:
and quietly [Didacus] passed to his eternal reward. It was November 12, 1463. King Philip II, of Spain, joined the people in soliciting the canonization of the servant of God. Rome heeded the petition and the usual rigid examination into the life of the friar began. [...] Finally, unmistakable proof having been presented that through the intercession of Venerable Didacus at least two miracles, that is works such as only God can effect, had been wrought, Pope Sixtus V, in 1588, placed his name in the catalogue of saints.
Not very helpful either.
PS: the Advocatus Diaboli title was later changed to that of Promotor Fidei.