Web-based learning provides the educational environment where learners can implement cooperative learning, knowledge sharing, and problem solving. Each student has his/her different knowledge or advantages, their mutual knowledge sharing behaviors can not merely give them opportunities to absorb the community members’ knowledge on the e-learning platform, but make them much closer. Although web-based instruction has been promoted and implemented in every university for years in Taiwan. Nevertheless, the discussion of students’ knowledge sharing behaviors with the employments of e-learning platforms is rare. Recent studies regarding the shaping of behaviors and behavioral intention, Theory of Planned Behavior is the most widely adopted. It is used in this paper to research on the causes for which students exercise knowledge sharing through e-learning platform. Furthermore, the discussion of psychological process appeared to lack in the earlier studies,so the influence of psychological safety will also be discussed. So, the purpose of this paper is to discuss: (1) the essential elements to form knowledge sharing intention; (2) knowledge sharing intention influences the generation of knowledge sharing behavior or not; (3) the influence of psychological safety on knowledge sharing intention. In order to test and verify the theoretical model used in this paper, questionnaire survey was used. Five hundred and eighty-four students of NCUE involved in the survey study, and four hundred and fifty-seven valid questionnaires were returned. The rate of return was 78%. Structural Equation Models were used to test research hypotheses, the result is partially different in related research. We found that except the relationship between attitude and behavioral intention isn’t signficant, both subjective norm and perceived behavioral control could affect the students’ behavioral intention toward knowledge sharing on the e-learning platform. We also found that psychological safety would help to form the knowledge sharing intention, and knowledge sharing intention is the predictor of knowledge sharing behavior. Based on these results, we gave our conclusions and concrete recommendations for higher education management and future research.