Design of the catalyst for efficient water dissociation and hydrogen recombination is paramount in enhancement of the alkaline water electrolysis kinetics.Herein,we reported a delicate hierarchical(VO)2P2O7-Ni2P@NF (VPO-Ni2P@NF) hybrid catalyst that operated efficiently in alkaline media.The VPO and Ni2P respectively act as the water dissociation promoter and the hydrogen recombination cen-ter,which synergistically propel water adsorption/dissociation and H intermediates recombination.The resulting synergistic interfaces between VPO and Ni2P are verified to afford the catalyst an outstanding performance for hydrogen evolution reaction in alkaline media with an overpotential of 154 mV at 10 mA cm-2,Tafel slope of 65 mV dec-1,and remarkable durability.Furthermore,the catalyst presents the potential for overall water splitting.This work may shed fresh light on the high-performance electro-catalyst design and the application of VPO on water electrolysis.