Gqeberha resident Ayanda Tatu appeared in the East London Magistrate's Court on Wednesday for the murder of Sergeant Mphakameli Mazinywana.
The 48-year-old Mazinywana died in a hail of bullets on 18 June this year when two unknown gunmen entered his Old Payne Location home in Mthatha and fired several shots at him.
Tatu is facing charges of murder, armed robbery and possession of an unlicensed firearm, the Hawks said.
He was arrested on Tuesday at his Motherwell home in Gqeberha by the Mthatha Hawks Serious Organised Crime investigation team, SAPS Tactical Response and SAPS Flying Squad.
The case has been postponed to Friday for a formal bail application, and Tatu remains in custody.
Hawks spokesperson Captain Yolisa Mgolodela said Tatu was found in possession of a firearm and 12 rounds of ammunition.
After gunning down Mazinywana shortly after entering his home at 18:30, the gunmen fled, taking his service pistol as well.