"You look really good tonight!" he said as he took the trophy in his hands.
Twain, wearing a low-cut Missoni gown, had walked out to a standing ovation. "It's good to see all of you too," she told the crowd Wednesday at Nashville's Sommet Center. "I hope to be seeing a lot more of you."
Twain, 43, won the coveted entertainer of the year award in 1999, and was last at the CMA awards in 2004.
PEOPLE first reported that Twain was expected at the ceremony on Wednesday. Her presence marked the singer's first public appearance since announcing her separation from husband Robert "Mutt" Lange in May.
A Warm WelcomeOnce Twain arrived at the ceremony, the stars were buzzing.
Rick Diamond / WireImage
Former tourmate John Michael Montgomery sent his best wishes to the singer, telling PEOPLE, "I just hate the fact that she went through her trials and tribulations, and I hope that she comes back as strong as ever. If she puts her mind to it, you ain't going to stop her."
New artist of the year nominee James Otto, who also toured with Twain, praised her crossover appeal. "She opened up country music to so many people who had never listened to it before," he told PEOPLE. "She really made a mark on country music."
Martina McBride summed up everybody's excitement, telling PEOPLE, "I'm so glad she's here tonight."
Photo Special: Best Dressed Stars!
Photo Special: The Night's Best Moments
1999: Shania goes from rags to riches
Read about more country music stars!