As an important part of social travel, college students have long become the main users of the online car-hailing industry. It is highly necessary to explore the perceived behavior of college students waiting for the arrival time of online car-hailing to promote the new standardized development of online car-hailing industry. Firstly, an online questionnaire was conducted among 492 college students about their waiting behavior and perceived state. Second, Cronbach's $\alpha$ and confirmatory factor analysis were used to test the reliability and validity of the questionnaire. Finally, the perceived time is divided into three categories, and a discriminant model of the perceived waiting time of ride-hailing vehicles is established based on the discriminant analysis method. Classification results and influencing factors of the discriminant analysis are empirically analyzed. It is found that these 35 variables contained in the four factors of personal characteristics, environmental factors, waiting behavior and mobile devices will affect the perceived waiting time. In the same group of classification functions, waiting behavior has the greatest impact on perceived waiting time, followed by environmental factors, and the lowest is mobile devices. The research results provide effective support for exploring the specific factors and potential psychology affecting college students' perceived waiting time, and provide certain theoretical value and practical guidance for effectively improving the service level and attraction of online car-hailing.