Abstract: The organizational structure reform of coal mining enterprises is one of the development trends of China’s coal industry in recent years. In order to explore the impact of the organizational structure reform of coal mining enterprises on the unsafe behavior intention of miners, the work insecurity of miner was introduced as a mediator variable, and a questionnaire survey was conducted among 156 miners of Shanxi Lu’an Group Luning Coal Industry Co., Ltd. Using Amos 24.0 software, a structural equation model (SEM) was established to explore the effects of organizational expansion, organizational mergers, organizational restructuring, and organizational layoffs on the unsafe behavior of miners through job insecurity. The research shows that the organizational structure reform has a significant positive relationship with the insecurities of miners’ work; the work insecurity is positively related to the unsafe behavior intention; the work insecurity is the mediator of organizational structure change and miners’ unsafe behavior intention.