The 50-year-old hunk is planning to tie the knot with Angelina Jolie, who he got engaged to in April 2012, and is hoping the band - which includes brothers Caleb, Jared, Nathan and cousin Matthew Followill - aren't on tour on the big day.
The 'Sex On Fire' rockers have a few UK dates lined up for the summer, including headlining Isle Of Wight festival in June, and Brad it hoping they can make "dates work".
A source told The Sun newspaper: "Brad ended up partying with Kings Of Leon last week. He spent most of the night talking to Caleb and he sounded them out about playing.
"It will happen if they can make the dates work."
Brad and Angelina - who met on the set of 'Mr. and Mrs. Smith' in 2005 and raise six kids together - have been trying to arrange the ceremony at their French chateau for the past three summers, but other commitments have delayed their nuptials.
A source added: "It's been a long time coming but finally it is going to happen."
Brad partied with Kings of Leon following the band's Los Angeles gig last week.
The 'World War Z' star arrived at at Warwick bar and restaurant with 'The Curious Case Of Benjamin Button' writer, Eric Roth, and made a beeline straight for the rockers at their official afterparty, before heading home at around 3am.