The action epic, starring Daniel Craig as superspy 007, beat competition from Anna Karenina, The Best Exotic Marigold Hotel, Les Miserables and Seven Psychopaths to claim the coveted title on Sunday (10Feb13).
Accepting the honour, director Sam Mendes said, ""We all had high expectations for this film and this is really the icing on the cake.""
Skyfall, which has a total of eight BAFTA nominations, also picked up the prize for Best Original Music, thanks to its hit Oscar-nominated theme tune by Adele.
A handful of winners were announced prior to the ceremony kicking off at London's Royal Opera House, with prizes going to movie musical Les Miserables (Best Hair & Make-Up), Anna Karenina (Best Costume Design) and Brave (Best Animation).
Steven Spielberg's historical drama Lincoln led the nominees going in to the BAFTAs with 10 nods, while Les Miserables and Life of Pi both had nine.
The BAFTAs are set to be broadcast with a two-hour delay, airing on U.K. TV from 9pm local time.