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In the present study, we explored the effectiveness of PES-Ag₃PO₄/g-C₃N₄ film photocatalyst in degrading methyl orange dye under visible light irradiation. The PES-Ag₃PO₄/g-C₃N₄ film photocatalyst was prepared via a non-solvent-induced phase inversion process and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), laser scanning microscopy (LSM), X-ray photoelectron spectra (XPS), UV-diffuse reflectance (DRS), and water contact angle. The incorporation of the Ag₃PO₄/g-C₃N₄ composite into the PES matrix improved the pristine PES film’s hydrophilicity, as evidenced by the reduction of water contact angle from 79.03° to 54.33° for a film containing 15 wt % of Ag₃PO₄/g-C₃N₄ composite. The film’s photoactivity showed that 13 wt % was the best loading of Ag₃PO₄/g-C₃N₄ composite, and the degradation performance was maintained up to three cycles. The •O₂⁻ and h⁺ were the predominant species responsible for the methyl orange degradation.