Electrochemical oxidation based on SO4•- and •OH generated from sulfate electrolyte is a cost-effective method for degradation of persistent organic pollutants (POPs). However, sulfate activation remains a great challenge due to lack of active and robust electrodes. Herein, a B/N codoped diamond (BND) electrode is designed for electrochemical degradation of POPs via sulfate activation. It is efficient and stable for perfluorooctanoic acid (PFOA) oxidation with first-order kinetic constants of 2.4 h-1 and total organic carbon removal efficiency of 77.4% (3 h) at relatively low current density of 4 mA cm-2. The good activity of BND mainly originates from a B and N codoping effect. The PFOA oxidation rate at sulfate electrolyte is significantly enhanced (2.3-3.4 times) compared with those at nitrate and perchlorate electrolytes. At sulfate, PFOA oxidation rate decreases slightly in the presence of •OH quencher while it declines significantly with SO4•- and •OH quenchers, indicate both SO4•- and •OH contribute to PFOA oxidation but SO4•- contribution is more significant. On the basis of intermediates analysis, a proposed mechanism for PFOA degradation is that PFOA is oxidized to shorter chain perfluorocarboxylic acids gradually by SO4•- and •OH until it is mineralized.