In order to improve firing accuracy, the closed-loop fire calibration technology is widely used by modern weapon system. The photoelectric detection has advantages of good concealment and high precision. In this paper, a new calibration method based on photoelectricity was proposed, the theory of miss distance measurement was analyzed based on photoelectricity and the structure of the closed-loop calibration system, which could educe the miss distance automatically through the technology of digital image processing, such as smooth filter, image segmentation, diagnostic point selection. The simulation calculation was performed and proved the closed-loop fire calibration technology based on photoelectricity could improve fire calibration efficiency and firing accuracy, and reduce time for combat preparation.