The Sb-doped ZnO film/n-Si heterojunction is synthesized by simple chemical vapor deposition method. The quality of crystal and surface morphology of Sb-doped ZnO film are improved after annealing at 800 ℃, which exhibits effective p-type conductivity with a hole concentration of 9.56× 1017 cm-3. The properties of the p-ZnO/n-Si heterojunction photoelectric device are investigated. The resuets show that this device has good rectifier characteristics with a positive open electric of 4.0 V, and a reverse breakdown voltage of 9.5 V. The electroluminescent is realized at room temperature under the condition of forward current 45 mA. These results also confirm that the high-quality ZnO film can be prepared by the simple chemical vapor deposition method, which opens the way for simple preparation of materials applied to ZnO based opto-electronic device.