The present study attempted to examine the mediation effect of the career decision-making self-efficacy between the career barrier and the career aspiration among college students who were academically excellent high school students in South Korea. The results using correlation analysis showed that the career barrier negatively correlated with the career decision-making self-efficacy and the career aspiration, but the career decision-making self-efficacy positively correlated with the career aspiration. In addition, the result of structural equation modeling analysis preferred the complete mediation model over the partial mediation. Finding indicated that significant contribution of the career decision-making self-efficacy in the relationship between the career barrier and the career aspiration among academically excellent college students. Suggestions for future studies and counseling education were made.