A pomegranate-like nanosphere structure of CeO2 was prepared by a simple one-step hydrothermal method, and the novel CeO2 structure was printed on a TiO2 film to form a scattering layer, which constituted the composite structure of a photoanode in a thin film optoelectronic device. Then ZnCuInSe quantum dots, a ZnS passivation layer and a CuS counter electrode were prepared, and these parts were assembled into quantum dot-sensitized solar cells. By changing the thickness of the scattering layer film in the photoanode, the quantum dots were adsorbed on TiO2 more effectively. By using the special ball-core structure, light was scattered so that the photoanode used the light many times, which effectively increased the efficiency of photoelectron production. After electrochemical testing of the device, it was found that the photoconversion efficiencies of the TiO2 transparent layer and the CeO2 scattering layer composite photoanode were greater than that of a single TiO2 photoanode without a scattering layer. The results showed that when the thickness of the scattered layer was 10 ± 1 μm, the highest photoelectric conversion efficiency (PCE) was obtained, which was 20% higher than that seen with TiO2 alone.