Tembo replaces Thomas Madigage who has joined Bafana Bafana as assistant to coach Gordon Igesund.
The former Zimbabwean national team defender has served Matsatsantsa for the past few years both as a player and a coach for the club's reserve team.
Meanwhile Maritzburg United striker Diyo Sibisi could find a new home at SuperSport next season.
Sibisi, who was transfer-listed by United a few weeks ago, started training with SuperSport today hoping to impress coach Gavin Hunt.
The striker previously played for Free State Stars, Ajax Cape Town and Mamelodi Sundowns before moving down to Pietermaritzburg to play for the People's Choice.
Sibisi has also been joined by an unnamed Egyptian defender who is also on trial.
The Gavin Hunt led side, which has signed Bevan Fransman, George Maluleka, and Mark Haskins so far, is expected to leave Pretoria today for Cape Town where they will hold their pre-season training.