The synthesis of Ce co-doped Ag–ZnO (Ce–Ag–ZnO) has been successfully achieved by a solvothermal method. The synthesized catalyst was characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) images, diffuse reflectance spectra (DRS), photoluminescence spectra (PL), cyclic voltammetry (CV) and BET surface area measurements. The photocatalytic activity of Ce–Ag–ZnO was investigated for the degradation of Napthol Blue Black (NBB) dye in aqueous solution under solar light irradiation. Co-dopants shift the absorbance of ZnO to the visible region. Ce–Ag–ZnO is found to be more efficient than Ag–ZnO, Ce–ZnO, commercial ZnO, prepared ZnO, TiO₂-P25 and TiO₂ (Merck) at pH 9 for the mineralization of NBB dye under solar light irradiation. The influences of operational parameters such as the amount of photocatalyst, dye concentration, initial pH on photo-mineralization of NBB have been analyzed. The mineralization of NBB dye has been confirmed by COD measurements. A degradation mechanism is proposed for the degradation of NBB under solar light. The catalyst is found to be reusable.