Mayambela had been with the Chilli Boys since 2017 after joining the club from Ajax Cape Town.
He was handed the captain's armband soon after his arrival to try and lead from the front as one of the senior players in the team.
Reports of Mayambela's possible departure from the Port Elizabeth-based side surfaced a few weeks, but neither the player nor Chippa United was willing to comment.
Mayambela is reportedly on his way back to the Free State to rejoin Bloemfontein Celtic.
The Chilli Boys took to their social media platforms to announce Mayambela's immediate departure from the club while wishing him well in his future endeavours.
Mayambela made 33 league starts for the Chilli Boys during his two-year stay with the club and found the back of the net on four occasions.
The 31-year-old leaves the club a few days after the retirement of Daine Klate, who will coach the club's MDC team for the upcoming season.
Mayambela is a journeyman, having played for no less than eight teams, including two stints with Chippa United.
He also played in Sweden for Djurgardens IF in 2014. The Cape Town-born player enjoyed great success at the Buccaneers between 2010 and 2013, but it was at Phunya Sele Sele where he really shone as a player for three consecutive seasons between 2007 and 2010.