Objective: To research on the relationship between core self-evaluation and career maturity of college students, and the chain mediating role of career motivation as well as coping style. Methods: Totally 400 college students completed the scale on college career maturity, core self-evaluations scale, career motivation scale, simplified coping style questionnaire. Results: (1)College students’ career maturity was significant positive associated with core self-evaluation, career intrinsic motivation and positive coping style; College students’ career maturity was significant negative associated with career extrinsic motivation and negative coping style; And college students’ core self-evaluation was significant negative associated their negative coping style. (2)Core self-evaluation can not only positively predict career maturity, but also indirectly affect college students’ career maturity through internal and external career motivation as well as positive and negative coping styles. Conclusion: Career motivation and coping style played a chain mediating effect between core self-evaluations and career maturity.