A novel Cu3(PO4)2/TiO2 nanoparticle (TNP)/CuO nanocomposite with an excellent natural solar-light-driven photocatalytic H2 production performance was synthesized using a sol-gel method. The 1%Cu3(PO4)2/TNP/CuO catalyst displayed a better photocatalytic H2 production yield (59.5 mmolg−1; natural solar light; 151 times higher than that of TNP under the optimal conditions; catalyst dosage of 0.010 g and 5% aqueous glycerol concentration) than TNP, CuO/TNP, Cu3(PO4)2/TNP, and various Cu3(PO4)2 loadings in the Cu3(PO4)2/TNP/CuO catalysts. The improved photocatalytic H2 yields could be attributed to a suppressed recombination of charge carriers, preferable visible absorption ability, crystallinity, strong interactions, and high surface areas of 1%Cu3(PO4)2/TNP/CuO, which were confirmed using X-ray diffraction, temperature programmed reduction, diffuse reflectance spectroscopy, transmission electron microscopy (TEM), high-resolution TEM, Brunauer-Emmett-Teller surface area analysis, elemental mapping, energy dispersive X-ray analysis, X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, Raman spectroscopy, photoluminescence, and photocurrent techniques. The 1%Cu3(PO4)2/TNP/CuO catalyst could also contribute to the enhanced photostability and recyclability towards the photocatalytic hydrogen production.