The article discusses the development of an innovative electrocatalyst, NiFe-sc-PBA, for the selective and efficient electrochemical oxidation of ethylene glycol (EG). This catalyst demonstrates high Faradaic efficiency of formic acid (FEFA) and robust stability even at low applied potentials, making it a promising solution for advancing green hydrogen production. The NiFe-sc-PBA catalyst has been shown to achieve current densities of 500 and 1000 mA cm−2 with FEFA reaching 98.5%, and maintaining stability over 50 hours at 1.60 V (FEFA > 90%). In situ/operando structural characterizations confirm the stability of Ni(II) sites during EG electrooxidation. Molecular dynamics simulations also indicate that EG molecules accumulate on the NiFe-sc-PBA surface, preventing reconstruction induced by hydroxyl species. When integrated into a coupled electrochemical hydrogen production system, the NiFe-sc-PBA catalyst significantly reduces cell voltage energy consumption by 450 and 530 mV at current densities of 1.0 and 1.5 A cm−2, respectively, compared to conventional alkaline water splitting systems. This not only enhances techno-economic efficiency but also facilitates the production of high value-added products. Impressively, the coupled system exhibits continuous operation at stepwise ampere-level current densities for over 500 hours without performance degradation, emphasizing the long-term stability and effectiveness of the NiFe-sc-PBA catalyst in green hydrogen production.