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Sunlight-induced photodegradation of rhodamine B over Ag3PO4 has been observed. Nanosized Ag3PO4 was synthesized by a facile ion-exchange route. X-ray powder diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, the Brunauer–Emmett–Teller surface area, UV–vis diffuse reflectance spectroscopy and photoluminescence spectra were employed to investigate the phase structure, morphology and optical property of the Ag3PO4 product. Nearly 100% of rhodamine B was degraded after a very short irradiation time using simulated sunlight in Ag3PO4 suspension, and the total organic carbon measurement revealed that a high degree of mineralization was achieved in the present photocatalytic system. Ag3PO4 catalyst has an excellent photocatalytic performance due to the high separation efficiency of electron and hole pairs. In the neutral pH solution, Ag3PO4 catalyst exhibited the best photoactivity under simulated sunlight. The photoinduced holes were considered to be the dominant active species in the photodegradation process.