This study employs qualitative research methods to delve into the psychological capital of college students at private institutions and its role in the entrepreneurship process. The findings indicate that the four core dimensions of psychological capital—self-efficacy, hope, optimism, and resilience—significantly influence the entrepreneurial behavior of college students. Through semi-structured interviews and participant observation with seven college students from private institutions who have entrepreneurial experience, the study reveals how these dimensions of psychological capital help students actively face challenges in entrepreneurship and promote their continuous development and success on the entrepreneurial path. The research emphasizes the importance of cultivating psychological capital in entrepreneurship education and proposes a series of recommendations for the cultivation of entrepreneurial psychological qualities in private institutions.