The construction of crystalline-amorphous coupling structure is one of the effective strategies to enhance the performance of oxygen evolution reaction (OER) and urea oxidation reaction (UOR). Herein, NiFe-LDH/NiMoO4/NF with high oxygen evolution and urea oxidation performance was successfully prepared by electrodeposition of amorphous substances on the crystalline precursor of hydrothermal synthesis. Remarkably, the NiFe-LDH/NiMoO4/NF displays exceptional electrocatalytic performance for OER and UOR, with a potential of only 1.57V vs. RHE at 100mAcm-2 and the Tafel slope of 54.4mV dec-1 for OER, high UOR activity with a potential of 1.45mV@100mAcm-2 and the Tafel slope of 20.4mV dec-1 in 1.0M KOH with 0.33M urea solution. In a hybrid acid-base electrolysis system for urea oxidation-assisted H2 production using NiFe-LDH/NiMoO4/NF as the anode electrode and Pt/C/NF as the cathode electrode, the process requires a cell voltage of only 0.55V vs. RHE at 10mAcm-2. Moreover, this hybrid acid/base system demonstrates stable operation for 110h with minimal attenuation at a current density of 100mAcm-2. These results indicate a facile strategy for the design of electrodes with crystalline-amorphous coupling structures for energy conversion.