Baloyi began his professional footballing career some 19 years ago, signing with Kaizer Chiefs, and went on to play for over 10 years with the Glamour Boys before making his move to the Brazilians in 2004.
In Chloorkop he enjoyed a highly successful six-year spell before hanging up his gloves in 2010, where he was then instilled in Sundowns' backroom staff.
However, the 38-year-old has now stepped down from his position at the club, although head of technical staff Trott Moloto says the door will always be open for the South African cult hero.
"Brian will continue to consult for Mamelodi Sundowns and will always be part of the Mamelodi Sundowns family," he said on the club's official website.
Baloyi made over 20 appearances for the South African national team between 1997 and 2008, featuring in the 1998 World Cup and 2000 Olympic Games in Sydney.