Ag3PO4/Cu2O composites were prepared by a facile wet chemical method. The specimens were examined by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and UV–Vis diffuse reflectance spectroscopy. The specimens exhibited an excellent photocatalytic activity on the degradation of RhB than pure Ag3PO4 and Cu2O. Furthermore, the photocatalyst specimen was found to exhibit higher efficiency in hydrogen conversion. It was found that a 30 wt% Ag3PO4-loaded specimen showed an excellent hydrogen generation performance. The excellent photocatalytic activity was ascribed to the separation of e–h pairs via the Z-scheme method composed of Ag, Ag3PO4 and Cu2O. This study demonstrated the potential approach to the photocatalytic splitting water to release hydrogen as well as the environmental purification of organic pollutants under visible-light irradiation.