Although the controversial film's director and star, Mel Gibson, was absent, the line-up included a number of other actors from the 1995 blockbuster, including Brian Cox.
Also on the red carpet outside the Dominion Theatre were actor-director Peter Mullan, who appeared as one of William Wallace's warriors, and Angus MacFadyen, who played Robert the Bruce.
All three spoke of their support for independence during a question and answer session ahead of the screening, which coincides with Braveheart's release on blu-ray, DVD and digital HD.
Gibson recorded a special video message for the audience, saying: "It is hard to believe that 20 years ago this month our production got under way in Scotland. And what a production it was."
Historians have criticised the film for a string of inaccuracies, but it proved to be a huge hit with cinema goers and scooped the Oscar for Best Picture.
Cox said: "Braveheart was a magnificent achievement for Mel Gibson, it was also a great honour and very unusual to film on one's own land.
"I haven't done many films here in Scotland, but to make a film on the scale of Braveheart was incredible."
Mullan, who played Veteran, said: "I'm delighted to be here as I didn't make the original premiere 20 years ago."