Novel 3D self-supported porous NiO@NiMoO4 core-shell nanosheets are grown on nickel foam through a facile stepwise hydrothermal method. Ultrathin NiO nanosheets on the nickel foam cross-linked to each other are used as the core, and tiny NiMoO4 nanosheets are further engineered to be immobilized uniformly on the NiO nanosheets to form the shell. This step-by-step construction of the architecture composed of ultrathin primary and secondary nanosheets efficiently avoids the agglomeration problems of individual ultrathin nanosheets. The ingenious architecture possesses the advantages of numerous diffusion channels for electrolyte ions, ideal pathways for electrons, and a large interfacial area for electrochemical reaction. The introduction of the NiMoO4 secondary nanosheets on the NiO primary nanosheets not only endows the heterostructure with high electrical conductivity and a large active area but also promotes an increase in oxygen vacancy content, which favors the improvement of electrocatalytic properties for the oxygen evolution reaction. The Tafel plot for the NiO@NiMoO4 core-shell architecture is as low as 32 mV dec(-1), and the overpotential needed to reach 10 mA.cm(-2) for NiO@NiMoO4 nanosheets is only 0.28 V.