The temperature effect on corrosion behaviors of PbCaSnCe alloy in 4.5M H2SO4 solution was investigated by using potentiodynamic curve, electrochemical impedance spectra (EIS), Mott–Schottky plot and photocurrent response methods. It was found that PbCaSnCe alloy was in passive state in sulfuric acid solution, a passive film can be formed on alloy surface. The compositions of passive films formed at 0.9V for 2h under different temperatures were detected by X-ray photoelectron spectroscopy (XPS). The results showed that the film resistance and the transfer resistance decreased with the increment of the solution temperature. Mott–Schottky analysis and the photocurrent response revealed that the passive film exhibited n-type semi-conductive character, the donor density of the passive film decreased with increasing the solution temperature. Photocurrent response revealed that the photocurrent increased with increasing temperature. XPS results indicated that the PbO2 content in passive films may increase with increasing the solution temperature.