Originally called the Best Country Vocal Performance, Duet, the award was first presented to Kenny Rogers and Ronnie Milsap at the 30th Grammy Awards in 1988 for the single "Make No Mistake, She's Mine". The next year, the category's name was changed to Best Country Vocal Collaboration, a name it held until 1996 when it was awarded as the Best Country Collaboration with Vocals. In 2011, the category was merged with the Grammy Award for Best Country Performance by a Duo or Group with Vocal and the Grammy Award for Best Country Instrumental Performance, forming the Grammy Award for Best Country Duo/Group Performance in order to "tighten the number of categories" at the Grammy Awards.
Alison Krauss holds the record for having the most wins in this category, with a total of five. She is followed by seven others, who have all won the award twice. Among the most nominated are Emmylou Harris and Willie Nelson, both nine-time nominees. Krauss has been nominated eight ties, while Dolly Parton was a seven-time hopeful. Nominated bands include 1996 winners Shenandoah, a five-man country music band, three-time nominees the Nitty Gritty Dirt Band, as well as one of the award's final recipients, the Zac Brown Band.