The entrepreneurship of college students is an important issue related to the harmony and sustainable development of society as a whole. At present, the existing research in the industry pays less attention to the influence mechanism of non-cognitive ability and social support perception on college students’ entrepreneurial intention. Using 450 survey data, this paper examines the relationship between non-cognitive ability and college students’ entrepreneurial intention in terms of five dimensions: openness, conscientiousness, extraversion, agreeableness, and emotional stability. At the same time, it focuses on the role of social environmental factors, namely, social support perception in the relationship between the non-cognitive ability and entrepreneurial intention, and explores the influence path. The results show that openness, conscientiousness, extroversion, and emotional stability have significant positive effects on entrepreneurial intention; agreeableness has no significant effect on entrepreneurial intention; openness, conscientiousness, extraversion, agreeableness, and emotional stability have significant positive effects on social support perception. The mediating effect of social support perception is as follows—it is part of the intermediary effect between openness, conscientiousness, extraversion, and emotional stability on entrepreneurial intention; within the influence of agreeableness on entrepreneurial intention, it plays a complete intermediary role. This paper enriches the research results on the impact of non-cognitive ability on entrepreneurial intention, reveals the intermediary effect of social support perception on the impact of non-cognitive ability on college students’ entrepreneurial intention, and broadens the field of vision for the study of college students’ entrepreneurial intention. The research results can provide a decision-making reference for the promotion of the entrepreneurial intention of college students, alleviating the employment pressure of college graduates in China and promoting sustainable economic development.