iO2 is an important material for photocatalytic oxidation to degrade organic pollutants, but its utilization under visible light is low, recovery is difficult, and stability is poor. We prepared ZrO2-TiO2/CoFe2O4 (Zr-Ti/Co) photocatalyst with hollow core-shell structure by sol-gel method and layer-by-layer self-assembly method with tetrabutyl titanate and Zirconium n-butoxide as main raw materials. The samples were characterized and analyzed by X-ray diffraction (XRD), transmission electron microscopy (TEM), solid ultraviolet visible diffuse reflection (UV-Vis DRS), fluorescence (FL), ultraviolet visible absorption (UV), vibrating sample magnetometer (VSM). It is concluded that the TiO2 maintains a good anatase phase structure in the Zr-Ti-Co photocatalyst. Under UV light and sunlight, the degradation rate of the photocatalyst reached 96.1% and 99.7% for 60 min, respectively, for Rhodamine B (10mg/L) reaction system. And after repeated use for five times, it still showed better regeneration and reuse.