For their 35th and final song at Bonnaroo, as a steady rain soaked Tennessee, My Morning Jacket eased into a cover of Mötley Crüe's "Home Sweet Home." It wasn't the only special moment during the four-hour, career-defining set — which included most of the band's new Evil Urges, killer covers of James Brown's "Cold Sweat" and Erykah Badu's "Tyrone," and a guest spot from Metallica guitarist Kirk Hammett ("an up-and-comer," said MMJ frontman Jim James), who shredded on the 2003 jam "One Big Holiday." "It was a loving affair," James said the next day, summing up the peaceful vibes floating around the festival. "And a magical night."

The covers-heavy set pointed at the musical paths the band has taken on Evil Urges, its fifth album, which amplifies its rootsy, anthemic indie rock with production that wouldn't be out of place on an Eighties Prince record. The disc, which hit the charts at Number Nine the week after the festival, earned the band its first appearance on Saturday Night Live. "When we got back to the dressing room, we were jumping on the couches and screaming like we'd just won a football game," says the 30-year-old James.

On Evil Urges, the Louisville, Kentucky, band shifts effortlessly from slow-burning love songs like "Thank You Too!" to the prog-rock-meets-R&B of "Highly Suspicious." "Sec Walkin," a blue-eyed-soul-style ode to taking walks, is especially close to James' heart. Before his recent move from Louisville to a one-bedroom apartment in New York, James took the same 90-minute stroll nearly every day. "It's very meditative," he says. "When the blood starts pumping, shit comes out. Rhythms come, lines come, melodies come. A lot of the songs on Evil Urges came from those walks."

"Getting those demos from Jim was like Christmas morning," says bassist Tom Blankenship, the only band member who's been in MMJ since the beginning. "Some of it's like, 'Oh, my God' — it's so good," adds drummer Patrick Hallahan, a six-year veteran who's known James since they were kids. "And some of it's like, 'What was he thinking?' You think you know somebody and then you're like, 'Man, maybe we should talk more!'"

A month before Bonnaroo, over lunch in New York, James is soft-spoken and careful with his words. Sometimes he unleashes a warm, wry smile. He grew up in Hikes Point, a suburb of Louisville. At three, he cried when he heard "When You Wish Upon a Star," and when he first laid his hands on a guitar, he was "completely captivated by it, like it could take me to another dimension." In seventh grade he got his own, and spent afternoons jamming on heavy metal and grunge at a drummer friend's house. He formed My Morning Jacket in 1998.

James won't get explicit about the meaning of his lyrics, but he admits Evil Urges' songs were written just before the collapse of a relationship. "I'd met this person who was really fantastic, and I got this wall of love that I hadn't felt in a while, and it brought out a lot of emotions," he says. "But it didn't work out. By the time we made the album, shit was falling apart. I was singing these really happy songs from a really sad place."