I think that the first time the canon of scripture was discussed in a council was at the Council of Laodicea sometime around 360 AD. I think that the exact date for this is rather uncertain. I think that the canon that was decided upon was the same as the protestant canon minus the Apocolypse. I am rather uncertain about these statements because I don’t have my sources readily available at the moment.
Anyhow, the next council to discuss the canon was the Council of Rome in 382, which, consequently is where we get our current Roman Catholic canon of Scripture. It was reaffirmed several times after that in various councils, letters, and documents (Council of Hippo 393, Carthage 397, etc.)
I do know that there was no council, ecumenical or not, that verified the protestant canon, although there were a very few early Church Fathers who, at one time or other, were in favor for a canon that matched the current protestant canon. But, the VAST majority of early Church Fathers and Councils affirm the current Roman Catholic canon.