This work aims to study the effect of redox property and surface morphology of perovskite oxides on the catalytic activity of CO oxidation and CO+NO reduction, with the redox property being tuned by doping Fe at the Co site of La0.8Sr0.2Co1‒xFexO3 and the surface morphology being modified by supporting La0.8Sr0.2CoO3 on various me-soporous silicas(i.e., SBA-16, SBA-15, MCF). Characteristic results show that the Fe doping improves the match of redox potentials, and SBA-16 is the best support of La0.8Sr0.2CoO3 when referring to the oxidation ability(e.g., the Co3+/Co2+ molar ratio). A mechanism for oxygen desorption from perovskite oxides is proposed based on O2-TPD experiments, showing the evolution process of oxygen released from oxygen vacancy and lattice framework. Cata-lytic tests indicate that La0.8Sr0.2CoO3 is the best for CO oxidation, and La0.8Sr0.2FeO3 is the best for CO+NO reduc-tion. The mechanism of CO+NO reduction changes as the reaction temperature increases, with XNO/XCO value de-creases from 2.4 at 250 °C to 1.0 at 400 °C. As for the surface morphology, La0.8Sr0.2CoO3 supported on SBA-16 possesses the highest surface Co3+/Co2+ molar ratio as compared to the other two, and shows the best activity for CO oxidation.