CMA Night's Best Moments!

Nicole Kidman wasn't just a presenter at Wednesday's CMA Awards – she was a supportive spouse too to double nominee Keith Urban. And what was she looking forward to? "Him!" she told PEOPLE. "Listening to him perform!"

While accepting the vocal group of the year award with his band Rascal Flatts, Jay DeMarcus couldn't help but point out the loudest thing onstage: his jacket! "I'm glad this happened fairly early in the show," he told the crowd of their win. "'Cause I gotta get mama's curtains back soon."

Two superstars in one shot! Brad Paisley and Keith Urban opened the show with double the sound in their first-ever live duet, performing their song "Start a Band."

After his kickoff performance, Brad Paisley had to get to his other job – helming the CMAs. Running onstage to join co-host Carrie Underwood, who introduced herself to the crowd, the singer joked as he was still fastening his tie, "I'm almost Brad Paisley."

Kellie Pickler unveiled her fierce breakup song "Best Days of Your Life," which she cowrote with pal Taylor Swift. Introducing the performance, host Brad Paisley joked of the collaboration, "Millions of teenage boys would give their left game controller to get into that writer's room."

Carrie Underwood brought down the house with her emotionally charged ballad "Just a Dream." But when she collected her female vocalist of the year award, she had a joke ready: "Mama, it's real hard to sing when you're in the second row crying!"

"I can't wait to see if he's wearing a shirt or not," Carrie Underwood quipped while announcing Kid Rock's performance of "All Summer Long." "I know the man can afford one." Guess what, Carrie? Not only was the rocker fully covered – he sported a jersey – but his special guest guitarist, the just-as-often shirtless Lil Wayne, wore a matching top!

Kenny Chesney was doubly honored: He was named entertainer of the year and accepted it from surprise guest Shania Twain. Taking in the big moment, the singer told Twain (in Missoni), "You look really good!"

Kenny Chesney celebrated the big night with someone special: dad David! The elder Chesney sat with his son during the ceremony, then the two continued the party at the Sony BMG bash (left). "The fourth is just as exciting as the first," Chesney told reporters about being the reigning entertainer of the year winner. "I know it won't go on forever, but I'm not quite ready to give this award up yet."

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