3DOM LaCoO3 and a series of A-substituted perovskite catalysts 3DOM La1-xCexCoO3 were prepared by PMMA template-excess impregnation method. The effects of Ce substitution on the microstructure, surface properties and redox properties of perovskite oxides were analyzed by XRD, BET, SEM, XPS, H2-TPR and the removal of toluene by catalytic combustion in air, and the optimal substitution ratio was finally determined. It can be seen that the 3DOM La0·7Ce0·3CoO3 sample has a complete macroporous structure, high specific surface area (35.6 m2 g−1), high Co3+/Co2+ and Oads/Olatt concentrations, good low-temperature reducibility, and outstanding catalytic performance at WHSV = 6000 mL/(g·h) (T50 = 103 °C, T90 = 204 °C). The results show that the excellent catalytic performance is closely related to the eminent morphology and structure of the catalyst, high surface adsorbed oxygen concentration and good reducibility.