Underwood, who earlier in the night won 'Collaborative Video of the Year' with Brad Paisley, took home the coveted 'Video of the Year' award for her song 'Good Girl'.
The singer thanked her fans as she accepted the award, saying: "We all love you. We all need you. Thank you so much for this."
Actress Kristen Bell and country singer Toby Keith presented the 11th annual broadcast of the fan-voted ceremony, which opened with a skit featuring President Barack Obama and his election opponent, Republican presidential candidate Mitt Romney.
Bell wowed the audience throughout the night by proving her genuine love of country music, even at one point singing her own version of 'Hell on Heels' by Miranda Lambert's band Pistol Annies.
Lambert herself took to the stage to perform early in the night, later winning the 'Female Video of the Year' award for her song 'Over You'.
Lady Antebellum's 'We Owned the Night' won the prize for 'Group Video of the Year'.
The band, who were nominated for two further awards, expressed deep gratitude to their fans for voting.
Lady Antebellum member David Haywood offered "huge thanks to CMT for connecting the dots with these things and playing these videos".
Tom Arnold and wrestler Steve Austin also made an appearance, presenting the award for 'Male Video of the Year' to Luke Bryan. The pair struggled to rip off their jacket sleeves in an effort to look "more country", with Arnold quipping: "I think I just ripped my Spanx."
There were 19 performances over the night by artists including Underwood, Willie Nelson, Pistol Annies, Kenny Chesney, co-host Toby Keith, Jason Aldean, Luke Bryan and The Band Perry.
Rascal Flatts closed out the show with a surprise performance of 'Don't Stop Believing' with Journey.
Watch the video for Carrie Underwood and Brad Paisley's 'Remind Me' below: