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Abstract Railway transportation of hazardous materials (HAZMAT) is common and is generally considered safe. However, transporting toxic, flammable, and explosive substances via railways carries significant risk due to their high volume, proximity to populated areas, low public awareness, and potential domino effect. Particularly, the practice has come into question after a Norfolk Southern train derailed in Ohio in February of 2023. This derailment continuously reminds the public and the industry that such incidents can profoundly affect a community, critical infrastructure, and the environment. To identify the root cause of the Ohio train derailment and discover the deficiency of the safety system applied, combining the cause mapping approach with the safety triad concept was employed in this study. Based on this approach and the preliminary incident investigation released by the National Transportation Safety Board, the incident sequence is established, and the causal events leading to this incident are identified in the three essential pillars of its safety system: prevention, mitigation, and response, respectively. The study subsequently develops recommendations to improve the safety system of HAZMAT freight trains. This is expected to lower further the probability and consequence of HAZMAT freight train incidents and ultimately result in long‐term changes in railroad transportation.