To solve the problems of suddenness, uncertainty and untimely emergency decision-making related to fire and explosion accidents in university laboratories, a combined method of BN and CBR is introduced to analyze laboratory accidents. By summarizing the characteristics of 72 accident cases worldwide, four scenario elements with key roles are extracted by combining the public safety triangle theoretical model; a BN is established from the macro perspective, which is based on the construction of dynamic scenarios; the evolution path is analyzed via BN theory; and the probability of occurrence of accidents is quantified from the microscopic perspective, with a focus on the analysis of the accidental evolution process. A case similarity calculation is carried out via CBR, and the construction of a BN-CBR-assisted decision-making model is completed, verified and corrected in an case study. The results show that the BN-CBR model can quickly determine the accident evolution path and the most similar historical cases, and its quantitative probability calculation enables one to comprehensively grasp the real-time state of the whole accident and the emergency response in a timely manner, which provides a new way to approach emergency decision-making of accidents.