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The working temperature of the faulty electrical equipment in the substation will be higher than its normal working temperature, and it is easy to cause fire. This paper designs a non-contact real-time fire early warning system. The system uses a long-wave infrared camera to perform non-contact grayscale imaging on the target. The host computer uses the LabVIEW software to collect images in real time and processes the image data to obtain the real-time working temperature of the electrical equipment in the substation. If this temperature value is higher than the maximum temperature for the safe operation of electrical equipment, the slave computer will alarm, and the staff can determine the fault location based on the image made by the system, and then eliminate the potential safety hazards in advance. The test results show that the system has a stable operation and an easy operation. The system can effectively monitor and accurately predict the operating status of electrical equipment in the substation, which greatly reduces the safety risks of workers and improves work efficiency.