A series of transition-metal LaBO3 perovskites (B = Mn, Fe, Co, Ni, Cu, and Zn) have been synthesized and tested as catalysts for the simultaneous removal of CO and NO in a fixed-bed reactor. To improve the catalytic activity, LaFeO3, the most active formulation, was modified by partially substituting other active metals (Mn, Co, and Cu) for Fe in the perovskite formulation (LaFe0.7M0.3O3). The results revealed that Mn substitution significantly improved the catalytic activity because it increased the Mn(IV)-to-Mn(III) ratio, leading to the generation of a large amount of structural defects, and also because it increased the amount of reducible active sites.