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Developing non-noble metal photocatalysts for efficient photocatalytic hydrogen evolution is crucial for exploiting renewable energy. In this study, a photocatalyst of Ni₂P/CdS nanorods consisting of cadmium sulfide (CdS) nanorods (NRs) decorated with Ni₂P nanoparticles (NPs) was fabricated using an in-situ solvothermal method with red phosphor (P) as the P source. Ni₂P NPs were tightly anchored on the surface of CdS NRs to form a core-shell structure with a well-defined heterointerface, aiming to achieve a highly efficient photocatalytic H₂ generation. The as-synthesized 2%Ni₂P/CdS NRs photocatalyst exhibited the significantly improved photocatalytic H₂ evolution rate of 260.2 μmol∙h⁻¹, more than 20 folds higher than that of bare CdS NRs. Moreover, the as-synthesized 2%Ni₂P/CdS NRs photocatalyst demonstrated an excellent stability, even better than that of Pt/CdS NRs. The photocatalytic performance enhancement was ascribed to the core-shell structure with the interfacial Schottky junction between Ni₂P NPs and CdS NRs and the accompanying fast and effective photogenerated charge carriers’ separation and transfer. This work provides a new strategy for designing non-noble metal photocatalysts to replace the noble catalysts for photocatalytic water splitting.