The most environmentally friendly method for producing hydrogen is through the electrolysis of water, reliable and effective catalysts play a crucial role in enhancing hydrogen production efficiency. In this paper, Fe–NiC2O4/NF in block form was prepared by hydrothermal method on nickel foam (NF) for electrolysis of water under alkaline conditions. The surface reconstruction of the Fe–NiC2O4/NF was further investigated via XRD, FTIR, and XPS during the oxygen evolution reaction (OER). The catalytic activity of Fe–Ni(OH)2/NiOOH formed after reconstruction was considerably enhanced in comparison to the original catalyst. The overpotentials for hydrogen evolution reaction (HER) at 10 mA cm−2 and OER at 100 mA cm−2 were 126 mV and 260 mV, respectively. Meanwhile, applying it in a two-electrode, total hydrolysis device only requires 1.53 V at 10 mA cm−2. This investigation introduces a novel method for surface reconstruction of electrocatalysts to facilitate electrolytic water reaction.