The Volunteer village is set up about 2 hours before kickoff. It is set up in the UC, which is upstairs from the bookstore near Neyland Stadium.
About 1hr 30min to 1hr 15 min before the game is the Vol Walk (must see). The band and then the players all come down from Gibbs Hall (athletic dorm), down Volunteer Blvd. to Peyton Manning Pass, and come out right at the front of the stadium.