M-N-C catalysts, incorporating non-precious-metal ions (e.g. M = Fe, Co) within a nitrogen-doped carbon support, have been the focus of broad interest for electrochemical O2 reduction and aerobic oxidation reactions. The present study explores the mechanistic relationship between the O2 reduction mechanism under electrochemical and chemical conditions. Chemical O2 reduction is investigated via the aerobic oxidation of a hydroquinone, in which the O-H bonds supply the protons and electrons needed for O2 reduction to water. Mechanistic studies have been conducted to elucidate whether the M-N-C catalyst couples two independent half-reactions (IHR), similar to electrode-mediated processes, or mediates a direct inner-sphere reaction (ISR) between O2 and the organic molecule. Kinetic data support the latter ISR pathway. This conclusion is reinforced by rate/potential correlations that reveal significantly different Tafel slopes, implicating different mechanisms for chemical and electrochemical O2 reduction.