The Khayelitsha-born player met with Ajax recently to ask the club to release him from his contract with the intention to join United.
Mayambela's contract with the Urban Warriors was due to expire in June next year but his aim is to rejoin Chippa, with whom he spent the first half of the 2015/16 season, as soon as possible.
According to a source close to Chippa, Mayambela is set to travel to Port Elizabeth on Monday to put pen to paper with the Chilli Boys.
"Ajax has agreed to release Mark and is heading to Port Elizabeth on Monday," said the source.
The former Orlando Pirates midfielder made 19 Absa Premiership starts for Chippa United last season, netting three times and bagging three assists.