Unsafe behaviours, such as violations of rules and procedures, are commonly identified as important causal factors in coal mine accidents. Meanwhile, a recurring conclusion of accident investigations is that worker states, such as mental fatigue, illness, physiological fatigue, etc., are important contributory factors to unsafe behaviour. In this article, we seek to provide a quantitative analysis on the relationship between the worker state and unsafe behaviours in coal mine accidents, based on a case study drawn from Chinese practice. Using Bayesian networks (BN), a graphical structure of the network was designed with the help of three experts from a coal mine safety bureau. In particular, we propose a verbal versus numerical fuzzy probability assessment method to elicit the conditional probability of the Bayesian network. The junction tree algorithm is further employed to accomplish this analysis. According to the BN established by expert knowledge, the results show that when the worker is in a poor state, the most vulnerable unsafe behaviour is violation, followed by decision-making error. Furthermore, insufficient experience may be the most significant contributory factor to unsafe behaviour, and poor fitness for duty may be the principal state that causes unsafe behaviours.