The development of entrepreneurship spirit among young people is instrumental in empowering and invigorating them to take up entrepreneurial activities and become entrepreneurs. Understanding the psychological motivations (behavioral intentions) for people to become entrepreneurs is essential for the development of requisite policy and for creating a sustainable environment for entrepreneurs to grow and survive. Grounded on the Theory of Planned Behavior (TPB), this paper examines the factors driving the entrepreneurial intentions of students by specifically examining how student internship motivations (SIM) moderate the impact of entrepreneurial attitude (EA), subjective norms (SN), perceived behavioral control (PBC), entrepreneurial education (EE), and entrepreneurial self-efficacy (ESE) on college students’ entrepreneurial intentions (SEI). A total of 478 valid responses gathered via a self-administered questionnaire from Chinese College students were analyzed with SPSS-26 by applying multiple linear regression analysis, moderation, and slope analysis. Results indicate that EA, SN, PBC, EE, and ESE positively influence college SEI. Most importantly, the moderation and slope analysis indicate that SIM significantly but negatively moderates the impact of EA, SN, PBC, and ESE on the entrepreneurial intentions of college students. SIM, however, failed to significantly influence the effect of EE on the SEI. The inferences (both academic and practical) of these discoveries for the development of sustainable entrepreneurial and internship programs are deliberated.