Electric bicycle riders, particularly youngsters, are one of the high risk groups of road transportation system. Previous studies were limited to the causes of electric bicycle accident, and failed to explore occurrence mechanism of accidents. For a better understanding of electric bicycle rider’s unsafe crossing behavior, a questionnaire which contains TPB variables such as intention, attitude, subjective norm and perceived behavioral control was made based on the theory of planned behavior (TPB). Electric bicycle rider’s unsafe crossing behavior model was established and tested by using AMOS 20.0 which is statistical software and can verify kinds of measurement model and path analysis model through structural equation modeling (SEM). Confirmatory factor analysis (CFA) and goodness-of-fit test indicates that TPB can well explain rider’s unsafe crossing behavior. The results show that attitude toward unsafe crossing and perceived behavioral control have a positive effect on unsafe crossing intention, while otherwise for. Perceived behavioral control and unsafe crossing intention do contribute to the prediction of unsafe crossing behavior. Available advices on the avoidance of unsafe crossing have been suggested on organizing safety education and training, increasing the traffic safety awareness of riders and strengthening law enforcement strategies.