In order to effectively prevent the rescue accidents of chemical enterprises and deeply explore the causes of the accidents, 27 rescue accidents of chemical enterprises are analyzed. It is clear that the rescue accidents mainly occurred in the rescue operation process of the confined space. According to the event time series, 24Model is used to analyze the rescue accident causes of chemical enterprises. The frequency of unsafe acts of the managers is higher than that of the direct operators. The high-frequency unsafe acts of the managers are failure to effectively carry out safety training, with a frequency of 43 times, accounting for 31.16%. The high-frequency unsafe acts of the operators include failure to take effective safety detection measures, failure to have operation qualification and failure to wear labor protection appliances. The research results show that measures such as normalized safety training and emergency drill, operation examination of special operators, operation safety requirements and on-site supervision of dangerous operation, scientific allocation and correct wearing of labor protection appliances can help to improve the accident prevention effect and effectively avoid the occurrence of rescue accidents in chemical enterprises.