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Organic–inorganic halide perovskites have shown great potential for the conversion of solar energy to hydrogen fuel via photocatalytic reaction due to their excellent optoelectronic properties. However, one of the biggest challenges for organic–inorganic halide perovskite materials in photocatalytic hydrogen evolution reaction (HER) lies in the serious recombination of photogenerated electron and hole pairs. Herein, we reported that the coupling of nickel phosphide (Ni2P) nanoparticles with methylammonium lead halide (MAPbI3) perovskite can significantly enhance the photocatalytic H2 evolution performance of MAPbI3. We found that Ni2P coupling can promote the electron exaction from MAPbI3, thereby accelerating the charge transfer and retarding the charge recombination. Moreover, Ni2P particles exhibited good electrocatalytic activity for the HER. Consequently, the Ni2P/MAPbI3 composite exhibited ca. 459 times higher activity than the parent MAPbI3 in photocatalytic HI splitting reaction. Moreover, the Ni2P/MAPbI3 composite exhibited excellent stability during cycling tests. This work demonstrated the potential of using Ni2P as non-noble metal-based co-catalyst to promote the photocatalytic performance of organic–inorganic halide perovskite. [ABSTRACT FROM AUTHOR]