With the increasing employment pressure of college students and the steady promotion of China's rural revitalization strategy, attracting college students to participate in rural revitalization has become an important issue. This study explores the relationship between rural volunteering, role identity, and career expectations of college students' rural volunteers, and provides a theoretical basis for improving college students' rural career expectations. A questionnaire survey was conducted among 266 college students, and the structural equation modeling and bias-corrected self-sampling methods were used to explore the logical relationship between college students' rural volunteering and career expectations, and to examine the mediating role of role identity in them. The results show that: (1) College students' rural volunteering helps to raise their career expectations in rural revitalization; (2) College students' rural volunteering can promote their role identity; (3) College students' volunteer role identity can positively influence career expectation; (4) College students' rural volunteering positively influences career expectations through the mediation of role identity.