The rational design of efficient catalysts can be guided by identifying proper descriptors that can rationalize and predict the catalytic behavior. This study presents the feasibility of using the relative positions of the O p-band center and the B-site metal cation d-band center as an activity descriptor for methane oxidation over LaCoO3 perovskite oxides. Experiments on B-site-substituted LaFexCo1-xO3 perovskite oxides revealed that the relative positions of the two band centers governed the catalytic comportment. The suprafacial model-driven catalysts with negative relative position values exhibited high activity at low temperatures. Conversely, the intrafacial model-driven catalysts with positive relative position values showed superior activity at high temperatures. These findings were found to be effective for catalytic performance prediction on the A-site substituted La1-xSrxCoO3 perovskite oxides. This work hence showcases a promising principle to design highly active perovskite catalysts suitable for oxidation reactions. (C) 2020 Elsevier Inc. All rights reserved.