Ethylene evolution reaction (EER) by electrochemical dechlorination of 1,2-dichloroethane is a promising and an economical strategy. The process is however severely impeded by the poor reactivity of catalysts, the accumulation of HCl in the electrolyte as well as low value-added by-products at anode. Herein, a bifunctional ultrathin Fe–Nx–C single-atom catalysts (SACs) has been successfully prepared and investigated as both cathode and anode material for EER and aromatic chlorination reaction (ACR), respectively. The generated HCl was recycled as a chlorinating reagent. The Fe–Nx–C SACs exhibited an excellent electrocatalytic performance simultaneously for both EER and ACR with high ethylene and para–chloroanisole selectivity obtained. The first-principles calculations indicated that Fe–N4 was the dominating catalytic active site for the generation of ethylene as well as para–chloroanisole. The coupling strategy of ACR at anode not only can accelerate the reaction rate of EER, but also provide a highly-efficient and atom-economical approach for the production of valuable ethylene and aromatic chlorides.