Explosion accidents of molten aluminium in contact with water during aluminium production often occur and may cause injury and death. In this paper, a fuzzy Bayesian network (BN) was employed to probabilistically analyse the explosion accident of molten aluminium in contact with water. A fault tree-Bayesian network (FT-BN) model was established in the cause-effect analysis of the explosion accident, including three processes: electrolysis, molten aluminium transportation and aluminium casting. Fifty-three nodes were proposed in the model to represent the evolution process of the explosion accident from failure causes to consequences. Furthermore, the occurrence probabilities of basic events (BEs) were determined by expert judgement with weighted treatments based on fuzzy theory. By giving certain occurrence probabilities of each BE, the probability of an explosion accident was estimated. Subsequently, importance measures were assessed for each BE, which could reflect the impact on the occurrence of the top event (TE), and the final ranks were provided. The results indicate that using wet ladles and tools, water on the ground, breakage of the tap hole, damage to the casting mould, and leakage of circulating water are five main problems that cause explosion accidents. Safety advice was provided based on the analysis results. This study can help decision makers improve the safety management of aluminium production.