Vehicle-pedestrian accidents are one of the main types of road traffic accidents in China because of their mixed traffic features. By analyzing the characteristics of vehicle-pedestrian accidents, the head injury criterion (HIC) was selected as a quantitative index of pedestrian head injury risk, and vehicle-pedestrian collision simulation tests were carried out using PC-Crash. From the collected test data, the multivariate relationship models between the HIC, vehicle speed, and collision angle were fitted for different vehicle types. A risk assessment method for vehicle-pedestrian accidents based on the HIC was proposed by the Fisher optimal segmentation algorithm. Finally, a new index for evaluating the accuracy of accident risk classification, the degree of error classification, was proposed to verify the validity of the accident risk assessment method. The results show that vehicle speed, collision angle, and vehicle type play a key role in pedestrian injury. Flat-headed vehicles are more likely to cause head injuries to pedestrians than high-headed and low-headed vehicles. Rear-end collisions cause more injuries to pedestrians than side collisions. The research results can provide guidance and a basis for accident liability determination, speed limit management, vehicle safety design, and human injury mechanism analysis.