Recently, Ag3PO4 has been shown to be a promising photocatalyst for the degradation of organic pollutants in wastewater. The hetero-composites between Ag3PO4 and other phosphate can help to enhance the dispersion of Ag3PO4 particles, improve the separation of photo-generated charges, and decrease the cost of photocatalyst. In this study, Ag3PO4/Ni-3(PO4)(2) hetero-composites were prepared by a cation exchange reaction for the first time using cheap Ni-3(PO4)(2) as starting materials, characterized with higher-magnification transmission electron microscopy (HRTEM), X-ray diffraction (XRD), UV-vis diffuse reflectance spectroscopy (DRS), Fourier transform infrared (FTIR) and photo-luminescence (PL) technique, and tested in photocatalytic degradation of phenol in water under visible light. The results show that the Ag3PO4/Ni-3(PO4)(2) composites prepared by cation exchange reaction consist of well dispersive Ag3PO4 particles on the surface of Ni-3(PO4)(2), and the size of Ag3PO4 particles is 3-5 nm, which is far smaller than that of pure Ag3PO4 and Ag3PO4/Ni-3(PO4)(2) composites prepared by coprecipitation method. The content of Ag3PO4 has significant influence on the photo absorption, photocurrent response and photo catalytic performance, and Ag3PO4/Ni-3(PO4)(2) composites with Ag3PO4 loading of 60 wt.% display the highest photocatalytic activity for the degradation of phenol under visible light among these samples. The enhanced photocatalytic activity of Ag3PO4/Ni-3(PO4)(2) is related to the small particle size of Ag3PO4 and efficient separation of electron-hole pairs. (C) 2015 Elsevier Inc. All rights reserved.