Electrocatalytic hydrodechlorination is a promising approach for simultaneous pollutant purification and valorization. However, the lack of electrocatalysts with high catalytic activity and selectivity limits its application. Here, we propose a palladium-palladium oxide (Pd-PdO) heterostructure for efficient electrocatalytic hydrodechlorination of recalcitrant chlorophenols and selective formation of phenol with superior Pd-mass activity (1.35 min