In order to achieve high efficiency, low energy consumption and green hydrogen production, nickel and iron layered bimetallic hydroxide (NiFe-LDHs@NF) nanosheet arrays were synthesized on foam nickel substrate by solvothermal method as self-supporting electrodes. Structurally, the NiFe-LDHs nanosheet array grows vertically on the porous nickel foam substrate, which provides a directional electron transport channel and avoids the masking effect of the adhesive on the active sites. At the same time, the ultra-thin properties of nanosheets not only provide a larger specific surface area, enhance the coordination unsaturation of surface atoms, bring higher surface energy and reactivity, but also shorten the mass transfer path which is beneficial to the rapid diffusion of reactants and timely desorption of products, and improves the rate and efficiency of catalytic reaction. The results show that NiFe-LDHs@NF exhibits excellent electrocatalytic performance of UOR. A high current density of 50 mA cm-2 can be reached at a potential of only 1.46 V(vs. RHE). Compared with OER, the potential decreased greatly by 140 mV. Moreover, NiFe-LDHs@NF shows the robust stability within 24 h. Theoretical calculation shows that the Bader charge of Ni site in NiFe-LDHs is -1.25 e, indicating that Ni site is more likely to lose electrons and form NiOOH active species with high valence Ni3+. Ni3+ has strong adsorption to urea and is the real active site of UOR reaction, which is beneficial to the rapid development of UOR reaction and the stable progress of subsequent deprotonation. In addition, the conversion process of the intermediates from *CONH2N to *CONHN on Ni3+ sites is the reaction determination step (RDS) of the whole UOR reaction, with an energy of only 2.48 eV. It can be seen that the UOR reaction is easy to occur on NiFe-LDHs@NF and the reaction rate is fast. This study provides a new idea for the application of layered bimetallic hydroxides in the field of hydrogen production coupled with the urea electrooxidation.