The anodic oxygen evolution reaction (OER) of hydrogen production from electrolytic water requires a high over potential to overcome the slow kinetics. Therefore, urea oxidation reaction (UOR) with a theoretical overpotential of 0.37 V was used to decrease the anodic overpotential. Hydrothermal and electrochemical deposition methods were used to construct heterogeneous core-shell structure NF@Ni3S4@CoFe-LDHs catalytic electrode which used in basic urea solution. Due to the synergistic effect of hierarchical structure and heterogeneous species at the interface, the adsorption of intermediate products and the desorption of protons on the electrode surface are accelerated, and the decomposition energy barrier of water and urea molecules is greatly reduced. In the mixed solution of x mol/L urea (x=0.1, 0.33 and 0.5) with 1mol/L KOH, it only need 100 mV overpotential to drive 10mA/cm² current density. In 0.33 mol/L alkaline urea solution, the NF@Ni3S4@CoFe-LDHs can driven 116mA higher than that in 1mol/L KOH solution, and it can operate stably for 20 h while maintaining good circularity. The catalytic electrode has good application prospects in hydrogen production from alkaline water and urea wastewater treatment.