Abstract Non-noble transition metal oxides are abundant in nature. However, they are widely regarded as catalytically inert for hydrogen evolution reaction (HER) due to their scarce active electronic states near the Fermi-level. How to largely improve the HER activity of these kinds of materials remains a great challenge. Herein, as a proof-of-concept, we design a non-solvent strategy to achieve phosphate substitution and the subsequent crystal phase stabilization of metastable β-NiMoO 4 . Phosphate substitution is proved to be imperative for the stabilization and activation of β-NiMoO 4 , which can efficiently generate the active electronic states and promote the intrinsic HER activity. As a result, phosphate substituted β-NiMoO 4 exhibits the optimal hydrogen adsorption free energy (−0.046 eV) and ultralow overpotential of −23 mV at 10 mA cm −2 in 1 M KOH for HER. Especially, it maintains long-term stability for 200 h at the large current density of 1000 mA cm −2 with an overpotential of only −210 mV. This work provides a route for activating transition metal oxides for HER by stabilizing the metastable phase with abundant active electronic states.