A TiO 2 @SiO 2 hybrid support was prepared by the sol-precipitation method using n-octylamine as a template. The photocatalyst manganese phthalocyanine tetrasulfonic acid (MnPcS) was immobilized on the support to form MnPcS-TiO 2 @SiO 2 . X-ray diffraction (XRD) and UV-Visible diffuse reflectance spectra (UV-Vis DRS) were employed to characterize the catalyst. The photocatalytic degradation of rhodamine B (RhB) and the catalytic oxidation of o-phenylenediamine (OPDA) under visible light irradiation were used as probe reactions. The mineralization efficiency and the degradation mechanism were evaluated using chemical oxygen demand (COD Cr ) assays and electron spin resonance (ESR), respectively. RhB was efficiently degraded by immobilized MnPcS-TiO 2 @SiO 2 under visible light irradiation. Complete decolorization of RhB occurred after 240 min of irradiation and 64.02% COD Cr removal occurred after 24 h of irradiation. ESR results indicated that the oxidation process was dominated by the hydroxyl radical (·OH) and superoxide radical (O 2 −· ) generated in the system.