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Underwood already wins two for Collaborative Video of the Year and Female Video of the Year, while Florida Georgia Line snatches Duo Video of the Year.
The song was co-written and recorded by the country singer for the upcoming comedy after Witherspoon personally asked her.
Despite losing the Entertainer of the Year title to Bryan, Lambert is still a big winner as she takes home multiple awards including Album of the Year for 'Platinum' and Female Vocalist of the Year.
After her 'Automatic' won Song of the Year earlier in the night, Lambert took home the Album of the Year title for its parent album 'Platinum'.
The songbird's 'Automatic' was named Song of the Year, while the country duo consisting of Brian Kelley and Tyler Hubbard won the Vocal Duo of the Year Award.
Lambert, Kellie Pickler and Jamie Lynn Spears show some skin in their gowns, while Witherspoon and her 'Hot Pursuit' co-star Sofia Vergara wear matching sparkling dresses.
The song titled 'Two of a Crime' which is expected to have a 'Southern and a Latin flavor' will be released on April 28, a week before the film opens in theaters on May 8.
The Academy of Country Music Awards will be made merry by Jason Aldean, George Strait, Reba McEntire, Keith Urban, Kenny Chesney, and more.
Pharrell Williams also stuns viewers with his performance of 'Happy' with pianist Lang Lang and film composer Hans Zimmer.
The wife of Blake Shelton is nominated for coveted titles including Entertainer of the Year and Female Vocalist of the Year.
Common, John Legend, and Usher will also take the stage at the Staples Center during the 57th annual music celebration.
Pregnant Carrie showed off her baby bump in a white tight long dress, Miranda bared her cleavage in a sheer black dress, while Cassadee looked elegant in a short-sleeved white gown.
The singer, who has also won Album of the Year, Single of the Year and Musical Event of the Year, is named Female Vocalist of the Year for the fifth time.
During 'Good Morning America' on Wednesday morning, November 5, the duo were announced as the winners in Musical Event of the Year category for their duet 'We Were Us'.
The country superstar bags nine nominations and is up for seven awards including Entertainer of the Year, Female Vocalist of the Year and Album of the Year.