The Catholic Church as a whole never accepted any formal canon in a full churchwide counsel until the counter-reformation. There we were some regional counsels in the 4th century that accepted the canon previously recognized; as recorded, for example, in Athanasius' 39th Festal letter.
Thats only partially correct. The councils of Carthage and Hippo in the 4th century were regional, but were ratified by Rome. See post 24.