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The stars will take part in the two-day music festival at Baton Rouge's Tiger Stadium over Memorial Day Weekend, May 26-27, 2012.
Rascal Flatts, Jason Aldean and Dierks Bentley join Underwood and Urban as headliners for the event.
Fellow country music hitmakers Sara Evans and Eric Church have been lined up for 'Bayou Country Superfest' as well.
Tickets will go on sale on October 20, with two-day passes ranging from $80 (£50) to $500 (£316) and single-day tickets running $50 (£31) to $250 (£158).
Aldean, Rascal Flatts, Underwood and Church have all received nominations for the American Country Awards, which airs Monday, December 5 at 8pm ET/PT on Fox.
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Watch Rascal Flatts perform 'Why Wait' below:
