Contemporary social reform promotes rapid social transformation, and social practice has a special educational function in higher education. However, research shows weak willingness to participate in social practice among college students. Using the mixed research method, 438 completed questionnaire surveys on perceived environmental support were collected from college students. The influence of perceived environmental support on Chinese college students’ willingness to participate in social practice was analyzed using partial least squares structural equation modeling, and an empirical test was conducted. The findings are as follows: (1) Perceived environmental support significantly impacts students’ participation attitude and perceived behavioral control. (2) Participation attitude and perceived behavioral control significantly influence participation intention, but behavioral norms have no significant influence. (3) Participation intention and perceived behavioral control significantly influence actual behavior. This study provides the theoretical basis of perceived environmental support for future research on social practice participation intention and offers some theoretical guidance for the implementation of social practice in China.