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To solve the inspection problems in cotton storage, as well as the need for environmental monitoring in the process of modern cotton bale storage, an intelligent inspection and temperature and humidity intelligent monitoring system based on RFID cotton bale was developed by adopting RFID (Radio Frequency Identification) technology, wireless temperature and humidity real-time monitoring technology and handheld terminal intelligent inspection technology. The system was composed of RFID positioning inspection module and temperature and humidity real-time monitoring and transmission module. The artificial neural network (ANN) based on the particle swarm optimization (PSO) algorithm was used to process the monitoring data of the system by Gaussian filtering, and an accurate classification model of RSSI and label position was established. The test results showed that: Through the comparative analysis of the RFID indoor positioning algorithm, the positioning error of the PSO-ANN algorithm was small. In the actual cotton bale warehouse test, the relative error of positioning and monitoring for RFID cotton bale intelligent inspection and monitoring system was less than 6.7%, which effectively improved the working efficiency of inspection personnel and the security of cotton bale storage. The relative error of temperature and humidity was less than 8% and less than 7%, which could display the temperature and humidity information in real time and meet the real-time demand. This study improved the management personnel's effective positioning and inspection of the cotton bale, prevented the loss of cotton bale, reduced the deterioration probability of cotton bale, and effectively improved the storage management level of the cotton bale. It was of great practical significance to realize the networking, automation, and intelligence of cotton bale storage management.