Multiple photoelectric sensors are designed for information fusion, in order to restrict the movement of robot end-effecter and camera, and then construct the hand-eye equation to obtain the corresponding hand-eye pose. First, the mathematical model of hand-eye calibration (HEC) is studied; moreover, the control system based on multiple photoelectric sensors with NImyRIO-1900 microprocessor as the core is designed. Its upper layer includes infrared sensor, acoustic photoelectric sensor, and gas photoelectric sensor, which can collect the position characteristics of the robot; finally, an automatic HEC system (HECS) is designed based on the control. The system combines the control system composed of multiple photoelectric sensors and the HEC method. It can collect data in real time, expand the camera field of vision, and improve the efficiency of HEC. When the calibration result reaches the predetermined accuracy, the HECS is terminated. In the experiment, the control system based on multiple photoelectric sensors helps the automatic calibration system to complete the picking task within 15 minutes. The success rate of pose planning of the end-effector of the system is 85%, the calibration attitude error is only 0.0586, and the position error is only 12.6685 mm, which verifies that the calibration system based on multiple photoelectric sensors is effective.