ZnS/CdS composite window layer was prepared by magnetron sputtering method and then applied to CdTe solar cell. The morphology and structure of films were measured. The data of Ⅰ-Ⅴ in light and the quantum efficiency of CdTe solar cells with different window layers were also measured. The effect of ZnS films prepared in different conditions on the performance of CdTe solar cells was researched. The effects of both CdS thickness and ZnS/CdS composite layer on the transmission in short wavelength were studied. Particularly, the quantum efficiency of CdTe solar cells with ZnS/CdS window layer was measured. The results show as follows. With the thickness of CdS window layer reducing from 100 to 50 nm, the transmission increase 18.3% averagely in short wavelength and the quantum efficiency of CdTe solar cells increase 27.6% averagely. The grain size of ZnS prepared in 250 ℃ is smaller than prepared at room temperature. The performance of CdTe solar cells with ZnS/CdS window layer is much better if ZnS deposited at 250 ℃. This indicates grain size has some effect on the electron transportation. When the CdS holds the same thickness, the transmission of ZnS/CdS window layer was improved about 2% in short wavelength compared with CdS window layer. The quantum efficiency of CdTe solar cells with ZnS/CdS window layer was also improved about 2% in short wavelength compared with that based on CdS window layer. These indicate ZnS/CdS composite window layer can increase the photon transmission in short wavelength so that more photons can be absorbed by the absorbent layer of CdTe solar cells.