Buster achieved All-American recognition at Oklahoma as a wide receiver.
Standing 6 ft 2 in (1.88 m) tall and weighing 218 lb (99 kg), Rhymes was selected by the Minnesota Vikings in the fourth round of the 1985 NFL Draft. Rhymes played in two National Football League (NFL) seasons for the Vikings in 1985 and 1986, and in 1985 set an NFL single-season record for kick return yardage with 1,345 yards; the league record has since been broken, but the total stood as a Vikings franchise record until broken by Cordarrelle Patterson in the final game of the 2013 season. Following his NFL stint, Rhymes went to Canada and played for the Winnipeg Blue Bombers of the Canadian Football League (CFL). He spent two seasons there (1988 and 1989), winning a Grey Cup championship ring in 1988.