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Exploring low-cost and highly active, cost-effective cocatalysts is of great significance to improve the hydrogen evolution performance of semiconductor photocatalysts. Herein, a novel ultrasmall V-doped NiP₂ nanoparticle, as an efficient cocatalyst, is reported to largely upgrade the photocatalytic hydrogen evolution reaction (HER) of g-C₃N₄ nanosheets under visible-light irradiation. Experimental results demonstrate that V-NiP₂ cocatalyst can enhance the visible-light absorption ability, facilitate the separation of photo-generated electron-hole pairs and boost the transfer ability of electrons of g-C₃N₄. Moreover, the V-NiP₂/g-C₃N₄ hybrid exhibits prominent photocatalytic HER activity 17 times higher than the pristine g-C₃N₄ counterpart, even outperforming the 1 wt.% platinum-loaded g-C₃N₄. This work displays that noble-metal-free V-NiP₂ cocatalyst can serve as a promising and efficient alternative to Pt for high-efficiency photocatalytic H₂ evolution.