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The sluggish kinetics of the oxygen reduction reaction (ORR) (cathode reaction) is a major bottleneck in the performance of polymer electrolyte membrane fuel cells (PEMFCs), thus requiring high active catalysts to enhance the kinetic rate of ORR.This article begins with a comprehensive overview of the theoretical mechanism study for the ORR, and ends with how to design a highly active catalyst for the ORR, especially the design based on theoretical calculations.