Electrochemical advanced oxidation processes (EAOPs) are promising technologies for perfluorooctanoic acid (PFOA) degradation, but the mechanisms and preferred pathways for PFOA mineralization remain unknown. Herein, we proposed a plausible primary pathway for electrochemical PFOA mineralization using density functional theory (DFT) simulations and experiments. We neglected the unique effects of the anode surface and treated anodes as electron sinks only to acquire a general pathway. This was the essential first step toward fully revealing the primary pathway applicable to all anodes. Systematically exploring the roles of valence band holes (h+), hydroxyl radicals (HO？), and H2O, we found that h+, whose contribution was previously underestimated, dominated PFOA mineralization. Notably, the primary pathway did not generate short-chain perfluoroalkyl carboxylic acids (PFCAs), which were previously thought to be the main degradation intermediates, but generated other polyfluorinated alkyl substances (PFASs) that were rapidly degraded upon formation. Also, we developed a simplified kinetic model, which considered all of the main processes (mass transfer with electromigration included, surface adsorption/desorption, and oxidation on the anode surface), to simulate PFOA degradation in EAOPs. Our model can predict PFOA concentration profiles under various current densities, initial PFOA concentrations, and flow velocities.