The issue of sudden water pollution resulting from accidents is a challenging environmental problem to address. The frequency of transport accidents involving hazardous materials over tributary bridges is steadily rising due to rapid industrialization and urbanization processes. This trend poses a significant threat to both the water’s ecological environment and human well-being. To effectively mitigate the risks associated with water pollution caused by accidents during the transportation of dangerous goods, this research focused on Baiyangdian Lake, the largest freshwater lake in North China. Thid study employed the expert judgment fuzzy language method and Bayesian network model as analytical tools to assess and analyze the potential risks associated with sudden water pollution accidents caused by the transportation of hazardous materials on bridges spanning tributaries. Through an examination of the various risk factors involved, the research identified four primary indicators and ten secondary indicators. Additionally, an oil leakage accident scenario was simulated, and recommendations for risk prevention and control measures were provided. The findings of the study indicated that: (1) The likelihood of risk associated with driver factors, vehicle emergency factors, fuel tank emergency factors, road factors, and lighting factors is elevated. (2) The probability of a dangerous goods transportation accident occurring on the Baiyangdian cross-tributary bridge is substantial, thereby presenting a potential hazard to both the water environment and human health. (3) Vehicle emergency factors, vehicle wear factors, and weather factors exert a significant influence on the incidence of accidents. (4) The highest likelihood of accidents is associated with a combination of factors, including driver fatigue, vehicle and fuel tank deterioration, and adverse weather conditions. (5) In instances where the vehicle and fuel tank are well-maintained, the probability of accidents is greatest on the cross tributary bridge, particularly when the driver is fatigued, weather conditions are unfavorable, and there is a lack of street lighting during nighttime. Implementing emergency prevention and control measures proved to be an effective approach in mitigating the risk of sudden water pollution accidents. This study offers valuable insights into risk mitigation and management strategies for emergent water pollution incidents, and the framework presented herein can be readily applied to other rivers worldwide confronting comparable risk challenges.