The main purpose of this research was discussing the relationship between athletic goals and self-confidence of college students' participation in volleyball games. This research collected data in questionnaire method; the research tools used by the researcher were divided into two parts: the athletic goal orientation inventory and the athletic self-confidence inventory, which were adapted from the referenced results from the researches of Li-Kang Chi (1994) and Kuo-Hsiung Cho (2002) for the research tools of this research. After acquiring the questionnaires, the researchers analyzed them with the structural equation model based on Amos 20.0; the result showed that the model of the research had a nice validity and fitness, and Ego Involvement of college students' participation in volleyball games had significantly influenced on their self-confidence, of which the path coefficient reached .34; Task Involvement had significantly influenced on their self-confidence, of which the path coefficient reached .24 According to the statistical analysis results of the research, the researcher made the discussion and proposed three suggestions to improve athletic goals of college students' participation in volleyball games to exert the positive influence on their self-confidence.