Targeting complete dechlorination and decomposition of chlorinated organic pollutants in an environmentally friendly and resource efficient manner. In this investigation, a three-dimensional multi-structured electrode (Pd-NC@Fe/CoCF) comprising Pd monatomic and nitrogen-doped carbon-coated FeCo2O4 nanowire cluster arrays were effectively synthesized. This electrode demonstrated efficient generation of H* and the production of •OH through a (2+1) e- oxygen reduction mechanism under the synergistic action of Pd single atoms and FeCo2O4 nanowire. When integrated with a square-wave pulsed electrocatalytic system, the chlorinated organic pollutants could be fully degraded within 45 min under the most favorable process parameters, which include a pulse voltage of −0.7 V, a duty cycle of 50 %, and a pulse frequency of 0.1 Hz. This results in a removal rate of 92.3 % for TOC and an energy consumption of 1.27 kWh·kg−1. This study presents a sustainable and environmentally friendly approach to the electrochemical degradation of chlorinated organic pollutants.