Brian Kelley and Tyler Hubbard earned prizes for Duo Video of the Year as well as Collaborative Video of the Year for This is How We Roll featuring Bryan.
The Drunk On You hitmaker landed a second award, CMT Performance of the Year, for a separate duet with Lionel Richie thanks to their Oh No/All Night Long set from the 2012 CMT Artists of the Year Tv special.
The trio dominated the show at the Bridgestone Arena in Nashville, Tennessee from the start of the ceremony, when they were joined by ZZ Top and R&B star Jason Derulo to sing and dance to a mash-up of his song Talk Dirty and Florida Georgia Line's This is How We Roll to kick off the programme.
It was also a big night for Carrie Underwood, Blake Shelton, and Miranda Lambert, who won the Video of the Year, Male Video of the Year and Female Video of the Year, respectively. This is the second year in a row in which the trio has taken the top honours.
The ceremony, which was hosted by three-time emcee Kristen Bell, also included sets from Keith Urban, Hunter Hayes, Dierks Bentley, Jake Owen, Lady Antebellum and Little Big Town.
John Legend sang a special version of his hit All of Me arranged by Hunter Hayes, while Sugarland's Jennifer Nettles joined in with vocals, and Lee Ann Womack and Kacey Musgraves took on Alan Jackson's Livin on Love just before Underwood presented him with the first-ever CMT Impact Award.
The top winners are:
Video of the Year - See You Again by Carrie Underwood
Female Video of the Year - Automatic by Miranda Lambert
Male Video of the Year - Doin' What She Likes by Blake Shelton
Group Video of the Year - Done by The Band Perry
Duo Video of the Year - Round Here by Florida Georgia Line
Breakthrough Video of the Year - Wasting All These Tears by Cassadee Pope
Collaborative Video of the Year - This is How We Roll by Florida Georgia Line featuring Luke Bryan
CMT Performance of the Year - Luke Bryan and Lionel Richie for Oh No/All Night Long from 2012 CMT Artists of the Year
CMT Impact Award - Alan Jackson