In this paper, we analyzed statistics about 142 accidents with hazardous materials that happened during the road transportation process in the past 20 years. The characteristics and laws of these accidents were summarized from the time of occurrence, the cause of the accidents, the type of Hazmat/road, and the physical appearance. The results showed that the accidents had unique time-phase characteristics, were especially likely to occur in March and December, and were particularly frequent at 9 am. More than half of the accidents were related to flammable liquids, and most led to leakage. Human factors are the most common causes of accidents.