The three-hour show -- televised live on CBS from the Grand Ole Opry -- opened with veteran duo Brooks & Dunn performing their single, "Only In America," with a huge American flag as a backdrop.
The pair later took home the award for top duo, their ninth win in that category in the past 10 years.
Popular singer Tim McGraw was one of several upset winners, taking home the prize for entertainer of the year. McGraw beat out industry superstars Dixie Chicks, Alan Jackson, George Strait and Brooks & Dunn.
Toby Keith and Lee Ann Womack were surprise winners for male and female vocalists.
"I can remember watching the awards show every fall when I was little," a tearful Womack told the audience, "and this was the award I wanted."
Womack performed her current single, "Does My Ring Burn Your Finger," the Buddy and Julie Miller bluegrass standard, with the Millers accompanying Womack.
Womack's was one of several bluegrass songs performed throughout the evening, with the bluegrass motif present in award winners as well.
"O Brother, Where Art Thou?," the soundtrack for the film of the same name starring George Clooney, won the coveted album of the year honors. A song from the album, "I Am A Man Of Constant Sorrow," performed by the Soggy Bottom Boys, won for single of the year.
Sara Evans, who led the field with eight nominations, won for best video for "Born To Fly."
"This is my first award ever," Evans said excitedly.
Australian keith urban took home the Horizon Award, given to the country artist most likely to succeed.
Vocal group Lonestar won their category over the popular Dixie Chicks.
The show, which was performance heavy, included a segment with Garth Brooks and George Jones, both in rare CMA Awards Show appearances. Brooks and Jones sang "Beer Run," a duet that both have included on their respective albums.
Perhaps the most memorable part of the show occurred when Jackson performed for the first time a song that he wrote last week. The song, "Where Were You That September Day?" recounted the many thoughts and emotions likely felt throughout the world in response to the September 11 terrorist attacks in New York and Washington D.C.
Celebrity Families of 2014 [PHOTOS]