The work aims to prepare Cu2O/TiO2 multilayer composite thin films with good photocatalytic properties. The Cu2O/TiO2 multilayer composite thin films were fabricated on the glass substrates by the direct current magnetron sputtering (DMS) technique and energy filtering direct current magnetron sputtering (EFMS) technique. The surface morphology, structure, transmission and photocatalytic properties of the films were characterized and analyzed by Field Emission Scanning Electron Microscope (FESEM), X-ray Diffraction Spectrometer (XRD), ellipsometer and photocatalytic test system. Both TiO2 and Cu2O thin films prepared by DMS and EFMS techniques were well-crystallized, but TiO2 had single anatase phase. Compared with the Cu2O thin films fabricated by DMS technique, Cu2O samples prepared by the EFMS technique had weaker diffraction peaks. The width of the diffraction peaks became wider and the diffraction curve was smoother. The surfaces were flatter and consisted of smaller particles with obvious boundary. For the thin films prepared by the DMS and EFMS techniques, the average crystal grain diameter was 15.4 nm and 10.8 nm, respectively. From the transmission spectrum test results, the average transmittance of the composite films prepared by EFMS technique was larger, namely 0.388 in the range of 350 nm to 800 nm, and that of the films prepared by the former was 0.343. The results of photocatalytic degradation for RhB indicated that the degradation rate of the films prepared by EFMS technique was -0.00411, larger than that (-0.00334) of the films prepared by DMS technique. Cu2O/TiO2 multilayer composite thin films prepared by the EFMS technique have higher photocatalytic degradation rate on RhB.