Enhanced light absorption and effective separation of photogenerated charges are the main strategies to improve the performance of photocatalytic materials. In this study, Ag3PO4/N-doped BiPO4 (N-BiPO4) core–shell structure photocatalyst was synthesized by a simple in-situ growth strategy in an organic solvent. The separation of photogenerated electron–hole was enhanced by the doping of nitrogen, because of the emergence of N–O impurity energy levels. The increased photocatalytic activity of Ag3PO4/N-BiPO4 could be attributed to the in-situ formation of chemical bonds between Ag3PO4 and N-BiPO4, which accelerate the separation of electron–hole pairs. The photocatalytic performance of the as-synthesized Ag3PO4/N-BiPO4 was evaluated by monitoring the decolorization of methyl orange under sunlight irradiation. Ag3PO4/N-BiPO4 was capable of bleaching 95% MO within 40min.