Background: Although hydraulic support can help enterprises in their production activities, it can also cause fatal accidents. Methods: This study established a composite risk-assessment method for hydraulic support failure in the mining industry. The key basic event of hydraulic support failure was identified based on fault tree analysis and gray relational analysis, and the evolution mechanism of hydraulic support failure was investigated based on chaos theory, a synthetic theory model, and cause-and-effect-layer-of-protection analysis (LOPA). Results: After the basic events of hydraulic support failure are identified based on fault tree analysis, structure importance (SI), probability importance (PI), critical importance (CI), and Fussell–Vesely importance (FVI) can be calculated. In this study, we proposed the Fussell–Vesely–Xu importance (FVXI) to reflect the comprehensive impact of basic event occurrence and nonoccurrence on the occurrence probability of the top event. Gray relational analysis was introduced to determine the integrated importance (II) of basic events and identify the key basic events. According to chaos theory, hydraulic support failure is the result of cross-coupling and infinite amplification of faults in the employee, object, environment, and management subsystems, and the evolutionary process has an obvious butterfly effect and inherent randomness. With the help of the synthetic theory model, we investigated the social and organizational factors that may lead to hydraulic support failure. The key basic event, jack leakage, was analyzed in depth based on cause-and-effect-LOPA, and corresponding independent protection layers (IPLs) were identified to prevent jack leakage. Implications: The implications of these findings with respect to hydraulic support failure can be regarded as the foundation for accident prevention in practice.