Abstract The reduction of electrodes coated with C 60-fullerene is examined in acetonitrile solution containing a wide variety of supporting electrolytes (MClO 4; M = Li, Na, Ba 0.5, NR 4). Electrochemical intercalation is observed with the formation of fulleride salts. Intercalation is typically irreversible except for the case of R = n-butyl where stable coats of fullerides may be formed into which charge can be passed with near chemical reversibility. Electron-transfer reactions at electrodes modified with C 60 coatings were investigated for diverse substrates. With unreduced coats impeded diffusion to the metal surface was seen, whereas with films reduced in the presence of tetrabutylammonium perchlorate coat-mediated electron transfer to the substrate was possible.