Poly(vinylferrocene)-graft-poly( propylene sulfide) copolymers have been synthesized and were used to form surface-modified gold electrodes (SMEs) by self-assembly and drop-evaporation techniques. The electrochemical behaviours and stabilities of the polymer films in the SMEs in 1 M H2SO4 media were investigated by cyclic voltammetry. The SMEs exhibited the expected electrochemical response and it was confirmed that the electron-transfer reactions occurred on the surface of the electrode. Repeated cycling of new SMEs indicated that films containing sulfur groups were more robust than similar SMEs based on simple poly(vinylferrocene). The stability of the SMEs increased with increasing proportions of propylene sulfide in the graft polymers.