The electrochemical oxidation of anodic copper in an acetonitrile solution of RSH (R= Ph, C10H7, CPh3, C6F4H, o-MeC6H4, CMe2Et) yields CuSR; treatment of CuSCMe2Et with CS2 produces Cu8 (SR) 4 (S2CSR) 4, whose structure is based on an unusual Cu8S12 cage.