FTIR spectroscopy of adsorbed NO revealed a variety of types of coordinatively unsaturated surface cations for lanthanum cobaltites, manganites, and ferrites, some of which emerge due to room-temperature surface reduction by the test molecule. For the surface of LaFeO3, clusters of coordinatively unsaturated Fe2+ cations associated with surface defects dominate. For the surface of LaCoO3 and LaMnO3, coordinatively unsaturated Me+3 cations are mainly revealed, being more coordinated by oxygen for the former system. These results could be used to analyze the catalytic properties of perovskites in the reaction of CO oxidation, provided the density of surface sites and reaction mechanism are taken into account.