The Amakhosi announced the appointment of the former Maritzburg United defender at a press conference Monday.
Paintsil, 35, replaces Doctor Khumalo as the second in command of the technical team headed by Steve Komphela at Chiefs.
Khumalo, the club says, will be redeployed.
Emmanuel Letlotlo has also been promoted to the 1st team while Alex Revoredo and Marco Muhnoz arrive as goalkeepers’ and physical trainers respectively. Brian Baloyi remains part of the goalkeeping department, Kaizer Chiefs also announced.