Ag₃PO₄ was prepared by the precipitation method using monobasic/dibasic phosphate salts (K₂HPO₄, KH₂PO₄, Na₂HPO₄, NaH₂PO₄) as a precipitating agent. The environment created by the precursor salts strong affected on the crystallinity and the morphology of Ag₃PO₄. Ag₃PO₄ synthesized from dibasic phosphate salts exhibited pseudospherical morphology and small particle size while monobasic phosphate salts promoted crystallization, resulting in a large grain size and a very diverse grain morphology. Ag₃PO₄ prepared from dibasic phosphate salts (K₂HPO₄ and Na₂HPO₄) exhibited superior photocatalytic ability, completely degrading rhodamine B (RhB) in 8 min and 10 min under Xenon lamp irradiation, respectively. This result once again confirms the necessity of particle size reduction in the production of photocatalysts.