The famous actress belted out "Country Strong," a tune from her forthcoming movie of the same name and wowed the crowd with her convincing performance at the 44th annual award show honoring the genre's top stars.
Accompained on-stage by crooner Vince Gill, Paltrow strummed an acoustic guitar as she poured her voice into the the song. Though she appeared nervous, she held her poise and gave a solid showing.
But when it came to the awards, the night belonged to Miranda Lambert. Her chart-topping album, "Revolution," captured the Country Music Association Award for album of the year.
Hailed by critics and musicians as the best album of the year, CMA voters agreed as "Revolution" completed a sweep of major country music awards Wednesday night on Lambert's 27th birthday.
"'Revolution' truly has caused a revolution in my life this year," Lambert said after a long hug with fiance Blake Shelton.
Lambert beat out her good friends Lady Antebellum for the coveted award and also won video of the year earlier in the night. Her song, "The House That Built Me," won song of the year for songwriters Tom Douglas and Allan Shamblin. The tale of a family's hard-luck times mirrors Lambert's own upbringing and has resonated with fans, spurring her to nine nominations.
Lady A had nothing to be blue about, riding their hit "Need You Now" to wins for single of the year and vocal group. The hit song about late-night hookups helped Lady A sell 3 million albums so far this year.
"Thank you to my brother, Josh Kelley, for making me to move to Nashville six years ago, I love you," Lady A vocalist Charles Kelley said after his band took single of the year.
Charles Kelley made the journey with his good buddy Dave Haywood and the two met Hillary Scott a short time later. The rest has been nonstop success with their second album, "Need You Now," selling more than 3 million copies this year.
The Zac Brown Band won new artist of the year.
Having some fun
Hosts Brad Paisley and Carrie Underwood joined Keith Urban to kick off the show with "Songs Like This" before the hosts returned to poke lighthearted fun at the stars and current events.
"Nashville had a flood and it barely made news," they sang, "while up through the gulf came a bubbling crude."
They also made fun at Tiger Woods and Brett Favre, singing, "She caught Tiger with some tail it's plain to see, and Brett Favre has taken up photography."
Paisley also finally won the CMA's coveted entertainer of the year trophy Wednesday night — besting another veteran and three relative upstart acts to make it happen. Paisley has been nominated for the award every year since 2005. Though he's won 13 CMAs since first being nominated in 2000, he's never won the biggest award until tonight.
He faced tough competition from former winner Keith Urban, Lambert, Lady Antebellum and Zac Brown Band, the first act nominated for both entertainer of the year and new artist since Ricky Skaggs in 1982.
Lambert will be partying hard with fiance Blake Shelton, who also got off to a fast start with a win in the musical event category for "Hillbilly Bone" with Trace Adkins.
"That's how I like to start the night," Shelton said. "Now I can get drunk and relax."
The entertainer of the year category underwent something of a makeover this year as the CMA membership installed a new wave of performers in key categories, acknowledging a crossover trend that is bringing country music to more new ears than ever.
The list of omissions in that category is long and includes Underwood, last year's winner Taylor Swift and several highly successful acts long considered contenders.
Still, there's no questioning the impact Lady A, Zac Brown Band and Lambert had on the industry over the past year.
"I got to make country music history, which is what everybody hope's for when they're in this industry, because I had the most nominations out of any female ever, so ... I'm having a great day already," she said, wearing a pink gown by Sherri Hill as she walked the black carpet. "It's my 27th birthday, so I'm hoping the best birthday would to take home obviously a CMA."
Lambert rode the popularity of her acclaimed platinum album "Revolution" to a record for the most nominations for a woman in the 44-year history of the CMAs and the second most overall. Both of her No. 1 hits, the sassy "White Liar" and "The House That Built Me," were nominated in two categories, song and single of the year.
The show was shown on ABC.