ABO3-type perovskites (A = La, Ce; B = Mn, Ni) were prepared by sol-gel method, and applied for catalytic oxidation of toluene. The activity test results show that the activity of LaMnO3 can be improved when a small amount of Ce and Ni are doped into the A and B sites of LaMnO3, respectively. The effects of different calcination temperatures and different calcination time on the preparation of La-based perovskites were also investigated. The results illustrate that the toluene conversion of La0.8Ce0.2Mn0.8Ni0.2O3 is the highest when the calcination temperature is 700°C and the calcination time is 4h in La1-xCexMn1-yNiyO3 perovskites, and it requires lower reaction temperature when the conversion rate of toluene reaches 100% as compared to other catalysts, the T90 is 295°C (T90, the temperature corresponding to the 90% of toluene conversion). Importantly, the mechanism of catalytic oxidation was also discussed. Therefore, the catalyst has potential prospects in the volatile organic compounds (VOCs) degradation.