Understanding the public transportation users' preferences to long-distance travel modes would contribute to reasonable developing policies and resource allocation. This paper aims to explore the influencing mechanism of potential factors on the long-distance travel mode choice. A survey was conducted to collect the data. The analysis of variance (ANOVA) approach was applied to analyze the correlation relationship between potential factors and travel mode choice behavior. The results showed that, except gender, service demand for safety and departure time, all of the other factors significantly influenced the travel mode choice behavior. Specifically, passengers with higher education level and income level were more likely to choose high-speed railway (HSR) and plane; passengers caring about travel expense were more likely to choose ordinary train, whereas plane and HSR may be chosen more by passengers caring more about comfort, punctuality and efficiency; the more passengers were satisfied with travel modes' service performance, the more they would be likely to choose them; the most competitive distance ranges for coach, ordinary train, HSR and plane were below 500 km, 500-1000 km, 500-1500 km and over 1500 km, respectively. Besides, the structural equation modeling (SEM) technique was applied to investigate the influencing mechanism of factors on the long-distance travel mode choice. The results revealed that travel distance was the most significant variable directly influencing passengers' mode choices, followed by the service demand, performance evaluation, and personal attributes. Furthermore, personal attributes were verified to have an indirect effect on travel mode choice behavior by significantly affecting the service demand and performance evaluation.