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Implementation of non-precious electrocatalysts is key-enabling for water electrolysis to relieve challenges in energy and environmental sustainability.Self-supporting Ni-V2O3 electrodes consisting of nanostrip-like V2O3 perpendicularly anchored on Ni meshes are herein constructed via the electrochemical reduction of soluble NaVO3 in molten salts for enhanced electrocatalytic hydrogen evolution.Such a special configuration in morphology and composition creates a well confined interface between Ni and V2O3.Experimental and Density-Functional-Theory results confirm that the synergy between Ni and V2O3 accelerates the dissociation of H2O for forming hydrogen intermediates and enhances the combination of H* for generating H2.