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Luke Bryan and Dierks Bentley's Buddy System: 'I Feel Like He's a Brother in a Lot of Ways,' Bentley Explains

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Luke Bryan arrives at a PEOPLE photo shoot before Dierks Bentley, and wastes no time taking advantage of his early entrance. Spotting a video camera, Bryan walks over, adopts a mock-serious tone and announces, “We’re here with PEOPLE magazine for the sexiest man issue. It was between me and Dierks, and they just informed me that I won!”

A short time later, both singers are taking turns cracking each other up and mugging for the camera. “Oh my God, we’re killing it!” Bryan declares as the two double over laughing.

Luke Bryan and Dierks Bentley
Perry Hagopian

The pair aren’t just the new hosting team for the Academy of Country Music Awards (airing April 3 on CBS), they’re also real-life longtime friends, having met as up-and-comers in 2005.

For the full story of Bryan and Bentley’s friendship and more from your favorite country stars, pick up the latest issue of PEOPLE, including the free Country insert.

“I feel like he’s a brother in a lot of ways,” says Bentley, 40, who says the two became close when Bryan was the opening act for his 2008 tour.

“We’d spend hours on the bus playing songs and we just had a great time,” Bryan, 39, says. “We trashed a couple of backstage areas.”

Adds Bentley, “I showed this guy how to throw a backstage party!”