Four novel two-dimensional porphyrin COFs (M-TP-COF, M = H₂, Co, Ni and Mn) with donor–acceptor dyads were fabricated and served as electrocatalysts for the oxygen reduction reaction (ORR). The ORR catalytic activity of M-TP-COF was tuned by changing the M atom in the center of the porphyrin backbone. The experimental structure–function relationship was in accordance with the results of density functional theory calculations based on the O₂–O₂*–OOH*–O*–OH*–OH⁻ route.