The musicians were joined by others including Mogwai and Fairground Attraction singer Eddi Reader for the show in front of 2,000 supporters in the country's capital Edinburgh.
The stars were performing to show their backing for Scotland breaking free from the U.K. ahead of the country's crunch vote on Thursday (18Sep14).
Other celebrities at the concert included Grey's Anatomy star Kevin MCKidd and actor Brian Cox.
Deacon Blue frontman Ricky Ross told Scotland's Daily Record newspaper, "Tonight reminds people we're nearly there but we're not there yet. Hopefully we're sending people away prepared for the last few days."