Human factors are important causes of hazardous chemical storage accidents, and clarifying the relationship between human factors can help to identify the logical chain between unsafe behaviors and influential factors in accidents. Therefore, the human factor relationship of hazardous chemical storage accidents was studied in this paper. First, the human factors analysis and classification system (HFACS), which originated from accident analysis in the aviation field, was introduced. Since some items were designed for aviation accident analysis, such as the item “Crew Resource Management”, it is not fully applicable to the analysis of hazardous chemical storage accidents. Therefore, this article introduced some modifications and changes to make the HFACS model suitable for the analysis of hazardous chemical storage accidents. Based on the improved HFACS model, 42 hazardous chemicals storage accidents were analyzed, and the causes were classified. After analysis, we found that under the HFACS framework, the most frequent cause of accidents is resource management, followed by violations and inadequate supervision, and finally the organizational process and technological environment. Finally, according to the statistical results for the various causes of accidents obtained from the improved HFACS analysis, the chi-square test and odds ratio analysis were used to further explore the relevance of human factors in hazardous chemical storage accidents. The 16 groups of significant causal relationships among the four levels of factors include resource management and inadequate supervision, planned inappropriate operations and technological environment, inadequate supervision and physical/mental limitations, and technological environment and skill-based errors, among others.