The present study investigates rod-like BiPO4 prepared by a hydrothermal process using bismuth nitrate and sodium dihydrogen phosphate as raw materials. Herein, Ag-AgBr was deposited onto the surface of BiPO4 via a facile precipitation-photoreduction technique. The structure, morphology, composition and optical property of as-synthesized samples were characterized by XRD, SEM, TEM, XPS, DRS and PL techniques. The results showed that introduction of Ag-AgBr did not change the structure and morphology of BiPO4, but extended its optical absorption to visible region. Moreover, the introduction of Ag-AgBr shifted binding energy of elements of BiPO4 to lower values, which implied that a strong interaction exists between Ag-AgBr and BiPO4. The photocatalytic tests showed that the Ag/AgBr/BiPO4 composites possess higher photocatalytic activity for degradation of anthraquinone dye (reactive brilliant blue KN-R) under simulated sunlight, as compared to that of pure BiPO4. The improvement of photocatalytic activity for Ag/AgBr/BiPO4 composites could be ascribed to their good optical absorption and the synergistic action between Ag-AgBr and BiPO4 substrate (the synergistic action effectively retarded recombination of photogenerated carriers in hetero-structured Ag/AgBr/BiPO4).