Metal–nitrogen–carbon (M–N–C) single-atom catalysts (SACs) have emerged as a potential substitute for the costly platinum-group catalysts in oxygen reduction reaction (ORR). However, several critical aspects of M–N–C SACs in ORR remain poorly understood, including their pH-dependent activity, selectivity for 2- or 4-electron transfer pathways, and the identification of the rate-determining steps. Herein, by analyzing >100 M–N–C structures and >2000 sets of energetics, we unveil a pH-dependent evolution in ORR activity volcanosfrom a single peak in alkaline media to a double peak in acids. We found that this pH-dependent behavior in M–N–C catalysts fundamentally stems from their moderate dipole moments and polarizability for O* and HOO* adsorbates, as well as unique scaling relations among ORR adsorbates. To validate our theoretical discovery, we synthesized a series of molecular M–N–C catalysts, each characterized by well-defined atomic coordination environments. Impressively, the experiments matched our theoretical predictions on kinetic current, Tafel slope, and turnover frequency in both acidic and alkaline environments. These new insights also refine the famous Sabatier principle by emphasizing the need to avoid an “acid trap” while designing M–N–C catalysts for ORR or any other pH-dependent electrochemical applications.