The effect of different Cu addition on the electrochemical and passivation behaviour of the 304 series stainless steel in 0.1 M phosphoric acid solution was evaluated by the potentiodynamic measurements and electrochemical impedance spectrum (EIS). The effect of Cu on chemical composition of the passive film formed in the solution was also studied by X-ray photoelectron spectroscopy (XPS). The results indicated that Cu did not appreciably improve the corrosion resistance of the passive film, but enhanced the passivation, lowered the critical and passive current density. The passive and critical current density decreased with Cu content increased. The presence of Cu in the passive film affects passive film stability. Cu can modify the proportion of Cr element in the passive film, and also change the components of Fe in the passive film. Copyright © 2012 John Wiley & Sons, Ltd.