- 1965 - Bonnie Owens & Merle Haggard
- 1966 - Bonnie Owens & Merle Haggard
- 1967 - Sons of the Pioneers
- 1968 - Johnny & Jonie Mosby
- 1969 - Kimberleys
- 1970 - Kimberleys
- 1971 - Conway Twitty & Loretta Lynn
- 1972 - Statler Brothers
- 1973 - Brush Arbor
- 1974 - Conway Twitty & Loretta Lynn
- 1975 - Conway Twitty & Loretta Lynn
- 1976 - Conway Twitty & Loretta Lynn
- 1977 - Statler Brothers
- 1978 - Oak Ridge Boys
- 1979 - Moe Bandy & Joe Stampley
- 1980 - Alabama
- 1981 - Alabama
- 1982 - Alabama
- 1983 - Alabama
- 1984 - Alabama
- 1985 - Alabama
- 1986 - Forester Sisters
- 1987 - Highway 101
- 1988 - Highway 101
- 1989 - Restless Heart
- 1990 - Shenandoah
- 1991 - Diamond Rio
- 1992 - Diamond Rio
- 1993 - Little Texas
- 1994 - The Mavericks
- 1995 - The Mavericks
- 1996 - Sawyer Brown
- 1997 - Brooks & Dunn
- 1998 - Dixie Chicks
- 1999 - Dixie Chicks
- 2000 - Dixie Chicks
- 2001 - Lonestar
- 2002 - Rascal Flatts
- 2003 - Rascal Flatts
- 2004 - Rascal Flatts
- 2005 - Rascal Flatts
- 2006 - Rascal Flatts
- 2007 - Rascal Flatts
- 2008 - Rascal Flatts
- 2009 - Lady Antebellum
- 2010 - Lady Antebellum
- 2011 - Lady Antebellum
- 2012 - Little Big Town
- 2013 - The Band Perry
- 2014 - Little Big Town
- 2015 - Little Big Town
- 2016 - Little Big Town
- 2017 - Old Dominion
The following are the winners for Best Vocal Duo in years where it was offered as a separate category:
- 1967 - Bonnie Owens & Merle Haggard
- 1980 - Moe Bandy & Joe Stampley
- 1981 - David Frizzell & Shelly West
- 1982 - David Frizzell & Shelly West
- 1983 - Kenny Rogers & Dolly Parton
- 1984 - The Judds
- 1985 - The Judds
- 1986 - The Judds
- 1987 - The Judds
- 1988 - The Judds
- 1989 - The Judds
- 1990 - The Judds
- 1991 - Brooks & Dunn
- 1992 - Brooks & Dunn
- 1993 - Brooks & Dunn
- 1994 - Brooks & Dunn
- 1995 - Brooks & Dunn
- 1996 - Brooks & Dunn
- 2000 - Brooks & Dunn
- 2001 - Brooks & Dunn
- 2002 - Brooks & Dunn
- 2003 - Brooks & Dunn
- 2004 - Brooks & Dunn
- 2005 - Brooks & Dunn
- 2006 - Brooks & Dunn
- 2007 - Brooks & Dunn
- 2008 - Sugarland
- 2009 - Brooks & Dunn
- 2010 - Sugarland
- 2011 - Thompson Square
- 2012 - Thompson Square
- 2013 - Florida Georgia Line
- 2014 - Florida Georgia Line
- 2015 - Florida Georgia Line
- 2016 - Brothers Osborne
- 2017 - Brothers Osborne
Most wins across both categories:
- Brooks & Dunn (16)
- The Judds (7)
- Rascal Flatts (7)
- Alabama (6)
- Conway Twitty & Loretta Lynn (4)
- Little Big Town (4)
- Bonnie Owens & Merle Haggard (3)
- Dixie Chicks (3)
- Lady Antebellum (3)
- Florida Georgia Line (3)
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