With the development of Internet technology, online car-hailing is booming in China, which has profoundly affected people’s travel structures. In order to seek the sustainable development of taxi and online car-hailing services from the perspective of passenger mode choice behavior, the mechanism of passengers’ decision-making procedures and their travel mode choice behaviors were analyzed. To study the influence of latent variable factors on passenger choice behavior, this paper firstly designed a questionnaire, and a structural equation model (SEM) was established for the preliminary study of the relationship between the latent variables and the behavioral intentions using the online survey data. Then, the latent variables were introduced into the Logit model, setting up the SEM-Logit model to explore the mode choice patterns between taxis and online car services. The results showed that the SEM-Logit model with the latent variables is better than a general Logit model in terms of the model precision and hit ratio. Meanwhile, after introducing the latent variables, it was found that convenience, comfort, and economy factors have a significant influence on the model, and the explanatory power of the model increases accordingly.