The 64-year-old will undertake his fourth job in the Absa Premiership, having also coached Mamelodi Sundowns, Kaizer Chiefs and Bloemfontein Celtic.
Dolezar will attempt to pull Black Aces away from the relegation zone after the side won just one of their 12 Absa Premiership matches to date, and sit second-bottom in the table.
He had enjoyed success at all the clubs he has coached so far. His last post in South African football was at Bloemfontein Celtic, where he won the Supa8 in his first weeks on the job but was fired after eight months.
He won the Absa Premiership as coach of Sundowns in 2000 and had a second spell in charge of the club from 2003 to 2005.
He was twice a Rothmans Cup winner with Kaizer Chiefs, where he first worked in South Africa in 1997.
Dolezar will be the third coach this season to lead AmaZayoni after the club have sacked Savvas Agiomamitis and then Neil Tovey in a matter of months.