Zolisa Maholwana, 45, was shot in the head and chest by a gang of robbers while waiting in his bakkie for his wife and nephew.
The incident happened shortly before midnight on Tuesday in the Newton Park SUPERSPAR car park between Second and Third Avenue.
The five suspects were arrested just minutes later.
Maholwana, who worked for the SBV cash-in-transit company, is believed to have run a sideline cash loan operation, commonly known as a “skopper”, with his wife from their Motherwell home.
The suspects were arrested in Newton Street after the K9 and Flying Squad units tracked them down.
The five, aged between 18 and 38, are believed to be members of the Spotbouers gang
The provincial Gang Investigation Unit has taken over the case.
It is unclear if Maholwana, who had his personal firearm with him, managed to shoot back during the attack. The alleged robbers’ bakkie was fitted with false number plates – belonging to the Makana Municipality – and the vehicle had been reported stolen last month in the Humewood policing area.