A series of LaNixB1-xO3 (B=Co, Cu) perovskite catalysts were prepared by sol-gel method and employed in toluene degradation. The catalysts were characterized by XRD, UV-Vis, SEM and XPS to investigate crystal structure, morphology and composition of the catalyst. The effect of different calcination temperatures and time on the performance of perovskite catalysts for toluene degradation were investigated. And the CO2 selectivity was also carried out on as-prepared catalysts. The results showed that a small amount of Co-doping in B site of LaNiO3 could significantly improve its toluene degradation, while the substitution of Ni with Cu could not effectively enhance its activity. When the Ni/Co molar ratio in LaNixCo1-xO3 perovskite was 3:1, LaNi0.75Co0.25O3 catalyst exhibited the best activity, and it showed relatively short time and low temperature for toluene conversion of 100%. Therefore, LaNi0.75Co0.25O3 catalyst has a broad prospect in the degradation of volatile organic pollutants.