This study aims to explore and understand the path of relationship among college students’ extracurricular activities, social relationship, and academic achievement to cultivate the competence of graduates’ employability due to the trend of fewer children. The results can help the school administrators to understand how to improve the administrative and teaching system to enhance the school’s competence for enrolling the new students. There are 8565 effective questionnaires data collected from the survey for junior in 92 study years and for one-graduated graduates in 93 study years through the Integrated Higher Education Databases System in Taiwan. Structural Equation Modeling methods was used to describe and analyze the information. The results revealed that joining the extracurricular activities is positive effective on social relationship and employability. But joining the extracurricular activities is negative effect on educational achievement. College students participating extracurricular activities can influence the competence of employability indirectly through the social relationship to be intermediary. Besides, the academic achievement can’t inf luence the competence of employability directly or indirectly. Moreover, the study sheds new lights on administrative, students and further researches in terms of enhancing competence of employability for college students.