This study explored the chain mediating role of perceived career barriers and career maturity in the relationship between social support and career adaptability of vocational college students. Eight hundred and sixty-two vocational college students were recruited to complete the Social Support Rating Scale, Perceived Career Barriers Inventory, Career Maturity Scale, and Career Adaptability Scale. Results indicated that: (1) social support could make significant positive effects on vocational college students' career adaptability; (2) career maturity could play a mediating effect on the relationship between social support and vocational college students' career adaptability; and (3) perceived career barriers and career maturity played a chain mediating effect between social support and vocational college students' career adaptability. It was concluded that social support can not only directly impact the career adaptability, but also make an indirect impact on the career adaptability of vocational college students through perceived career barriers and career maturity.