Acidic-stable oxygen evolution reaction (OER) catalysts based on earth-abundant materials are important but rare for the proton exchange membrane-based water electrolysis. In this study, a metal-containing hydrogen-bonded organic framework (HOF) of manganese coordinated with 2,2′-bipyridine-6,6′-dicarboxylate ligands, Mn(bda), interconnected through hydrogen bonding and π-π stacking was used as a heterogeneous OER catalyst (Mn(bda)-HOF) for acidic water oxidation and exhibited a considerable OER performance. Electrochemical results showed that Mn(bda)-HOF displayed a turn of frequency of 1 s−1 at an overpotential of 870 mV. Meanwhile, this Mn(bda)-HOF showed an unusual pH dependence on performance, where the reaction rate increased with the decrease in pH. A comprehensive mechanistic study reveals that the charge transfer triggered coupling of two metal-oxo species Mn5+(O) is the rate-determining step, which leads to this unusual pH dependence on the OER performance.