Herein, we investigate the electrochemical conversion of methane to CO2 on platinum electrodes under ambient conditions. Through a combination of experimentation, density functional theory (DFT) calculations, and ab initio kinetic modeling, we have developed an improved understanding of the reaction mechanism and the factors that determine catalyst activity. We hypothesized that the rate-determining methane activation step is thermochemical (i.e., CH4(g) → CH3* + H*) as opposed to electrochemical based on a fitted barrier of approximately 0.96 eV that possesses minimal potential dependence. We developed a simple kinetic model based on the assumption of thermochemical methane activation as the rate-determining step, and the results match well with experimental data. Namely, the magnitude of the maximum current density and the electrode potential at which it is realized agree with our ab initio kinetic model. Finally, we expanded our kinetic model to include other transition metals via a descriptor-based analysis and found platinum to be the most active catalyst for the oxidation of methane, which is in line with previously published experimental observations.