With the increasing demand of hazardous material (Hazmat), traffic accidents occurred frequently during Hazmat transportation, which had caused widespread concern in communities. Therefore, a good understanding of Hazmat transportation accident characteristics and contributing factors is of practical importance. In this study, 1721 Hazmat accidents that have occurred during road transportation for the period 2014–2017 in China were examined, and a random-parameters ordered probit model was established to explore the influence of contributing factors on the severity of accidents by accounting for unobserved heterogeneity in the data. Both the injuries and the number of people evacuated were considered as the indicator of accident severity and investigated, respectively. Results show that higher injury severity is likely to be associated with type of Hazmat (compressed gas, explosive, and poison), misoperation, driver fatigue, speeding, tunnel, slope, county road, dry road surface, winter, dark, more than two vehicles, rear end crash, and explosion. As for the correlation between risk factors and the severity of evacuation, type of Hazmat (compressed gas, explosive, and poison), quantity of Hazmat (10–39 t), misoperation, county road, dry road surface, weekdays, dusk, explosion significantly contribute to increasing the severity of evacuation of Hazmat accidents.