Mountainous freeways always suffer from accidents due to special terrain, weather conditions, driving environment, and so on. Based on the records of 898 accidents that occurred on mountainous freeways in Chongqing during the past 6 years, the partial proportional odds model is used to identify the factors affecting the accident severity. The time of the accident, season, involvement of trucks, accident characteristics, speeding, maximum driving experience of involved drivers, and weather and road conditions are found to be important for the levels of accident severity. Zero to 6 a.m. and 19 to 24 p.m. are the times prone to serious traffic accidents. The probability of serious traffic accidents in summer and autumn is greater than that in spring and winter. Once a truck is involved in an accident, the consequence is often more severe. Turnover and speeding will result in a grave accident. When there is an experienced driver, the probability of serious traffic accidents is low. The fog is extremely unfavorable weather conditions. The probability of serious accident happening in the downgrade, ramp, curve, bridge, and tunnel sections is greater than the others. The results aim to provide valuable reference for traffic safety on mountainous freeways.