Electron transfer through the self-assembled monolayers (SAMs) on gold nanoparticles is investigated by using the monolayer protected gold nanoclusters (MPCs) as electron-transfer mediators. 3-Mercaptopropionic acid (MPA) and 11-meraptoundecanoic acid (MUA) MPCs were employed to catalyze the redox reaction between potassium ferricyanide and sodium thiosulfate. The catalytic mechanism was proposed that the MPCs act as diffusing electron-mediators and electron transfers to and from the MPCs surface. Therefore the electron transfer rate through the capping layers would be proportional to the MPCs catalyzed reaction rate, which was monitored by the UV absorbance of ferricyanide. The calculated apparent rate constant was orders of magnitude smaller than that of the maximum of tunneling current, which was attributed to the splited energy level of the nanoscale particles.