Tailoring efficient and stable electrocatalysts based on non-noble metal elements for hydrogen evolution reaction (HER) is highly imperative for the commercialization of water splitting electrolysors. Herein, a self-standing core@shell Co@CoMoO4 nanowire array (Co@CoMoO4 NA) electrode is developed by calcination of a cobalt carbonate hydroxide@CoMoO4 (CCH NA@CoMoO4) precursor under H-2/N-2 atmosphere. In this way, synergistic Co/CoMoO4 heterostructure interfaces and 3D porous electrode architecture are built up, which are proved to be reliable strategies for HER catalytic activity enhancement. In 1.0 M KOH solution, Co@CoMoO4 NA electrode exhibits an impressive activity with an extremely low overpotential of 46 mV at 10 mA cm(-2), quite closing to that of commercial PtC (31 mV at 10 mA cm(-2)). These findings may inspire the exploration of new electrocatalysts for efficient HER by modulating multiple components interfaces.