Abstract: We recruited 821 college students and used questionnaire survey to measure their Big Five personality, environmental value, garbage sorting experience, and garbage sorting intention. The results showed that: ① Conscientiousness, agreeableness and extroversion of the Big Five personality positively predicted garbage sorting intention. ② Environmental values played a partial mediating role in the relationship between extroversion/conscientiousness/agreeableness and garbage sorting intention. ③ Garbage sorting experience moderated the mediating effect of environmental values on the relationship between extroversion and garbage sorting intention. However, garbage sorting experience did not moderate the mediating effect of environmental values on the relationship between conscientiousness/agreeableness and garbage sorting intention. Specifically, garbage sorting experience promoted the formation of environmental values of college students with high extroversion. The results imply that personality not only directly promotes the formation of college students' garbage sorting intention, but also improves their garbage sorting intention by shaping environmental values. Garbage sorting experience will accelerate the formation of this outcome.