A large number of universities worldwide are paying more and more attention to the application and exploration of online education. As the group with the most significant number of online education users, their participation attitude and participation intention directly determine the teaching performance of online education. This research will incorporate playfulness teaching and scenario variables that reflect the universities’ ability to respond to emergencies. Based on the technology acceptance model, this research proposes an integrated research model of online education participation intention to investigate university students’ online education participation intention to reveal the key factors and mechanisms that affect online education participation intention. A structural equation model of participation intention is constructed, and 342 valid samples are obtained by questionnaire survey. The empirical results of PLS-SEM show that: (1) students’ participation attitude positively affects their participation intention; (2) the perceived ease of use and usefulness positively affect their participation attitude, and the perceived usefulness and ease of use affect their participation intention through the complete mediation of participation attitude; (3) the perceived playfulness does not have a significant impact on participation attitude but has a positive impact on participation intention; (4) the innovative discovery university support positively moderates the relationship between participation attitude and intention during such emergencies. The research found that improving students’ attitudes toward participation, perceived ease of use, usefulness, playfulness, and strengthening university support are all helpful to optimize students’ participation intention in online education. At the same time, it also explored operability suggestions for improving the quality of online education and optimizing future education.