The Grammy-winning band will headline at the free event at Place des Festivals before the NHL season opener between the Montreal Canadiens against the Toronto Maple Leafs.
Bassist Jared Followill says they don't follow hockey "super passionately," but they do watch Predators games at home in Nashville and love the sport.
And they've become familiar with the Habs and the Leafs through friends.
"We know a lot about the Habs because our friends are in a (Montreal) band called the Stills, and they are like huge, huge Canadiens fans," Followill said Monday during a stop in Toronto to promote the new Kings of Leon album, "Mechanical Bull."
"And then Toronto Maple Leafs, we played at the ... Air Canada Centre and (goalie) Curtis Joseph came backstage and we played ping pong with him."
Followill said they're not rooting for either side.
"Right now I'm going to say the Maple Leafs, but when we land in Montreal I'll say the Habs," he said jokingly with a laugh. "We're Switzerland."
But at least one band member might wear a jersey once they hit the stage.
"Jerseys looks really good with skinny jeans, so that's going to be great," joked Followill.