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In this work, a simple chemical precipitation method was employed to prepare spherical-like Ag₃PO₄ material (IL-Ag₃PO₄) with exposed {111} facet in the presence of reactive ionic liquid 1-butyl-3-methylimidazole dihydrogen phosphate ([Omim]H₂PO₄). The crystal structure, microstructure, optical properties, and visible-light photocatalytic performance of as-prepared materials were studied in detail. The addition of ionic liquids played a crucial role in forming spherical-like morphology of IL-Ag₃PO₄ sample. Compared with traditional Ag₃PO₄ material, the intensity ratio of {222}/{200} facets in XRD pattern of IL-Ag₃PO₄ was significantly enhanced, indicating the main {111} facets exposed on the surface of IL-Ag₃PO₄ sample. The presence of exposed {111} facet was advantageous for facilitating the charge carrier transfer and separation. The light-harvesting capacity of IL-Ag₃PO₄ was larger than that of Ag₃PO₄. The photocatalytic activity of samples was evaluated by degrading rhodamine B (RhB) and p-chlorophenol (4-CP) under visible light. The photodegradation efficiencies of IL-Ag₃PO₄ were 1.94 and 2.45 times higher than that of Ag₃PO₄ for RhB and 4-CP removal, respectively, attributing to a synergy from the exposed {111} facet and enhanced photoabsorption. Based on active species capturing experiments, holes (h⁺), and superoxide radical (•O₂⁻) were the main active species for visible-light-driven RhB photodegradation. This study will provide a promising prospect for designing and synthesizing ionic liquid-assisted photocatalysts with a high efficiency.