Sexual health education is an essential part of quality-oriented education for college students. It aims to help these students to acquire knowledge of sexual physiology, sexual psychology, and sexual social norms that is consistent with the maturity of the students. Along with college students’attitudes toward sex, their perceptions regarding sexual behavior have also undergone profound changes. The importance of safe sexual behavior, sexual taboos, and sexual autonomy are gaining increasing attention as Chinese society is becoming more open. For college students who have just reached adulthood and have full autonomy of themselves, however, are they really going to have sexual behavior without careful consideration? Or is it something they have planned to do in the first place? To answer the above questions, this study was conducted to understand the relationship between college students’ attitudes toward sex, subjective norms, and behavioral control of their sexual behavior intentions by applying the Theory of Planned Behavior. In this study, 460 valid questionnaires were collected from Chinese college students and analyzed with partial least squares structural equation modeling (PLS-SEM). This study analyzes the relationship of multiple factors, including those influencing college students’ sexual behavior intentions. Meanwhile, it also compares the differences in factors affecting sexual behavior intentions between college students with or without sexual experience and those of different genders. Based on the results of the study, it was found that, first, subjective norms and perceived behavioral control of college students had a significant effect on safe sexual behavior intentions, while attitudes did not have a significant effect on safe sexual behavior intentions. Second, the gender and sexual experience of college students had a significant effect on safe sexual behavior intentions. Third, non-sexually experienced college students were more likely to be influenced by external factors. Relevant future research suggestions will be proposed based on the results of this study. Finally, this study helps to provide substantive suggestions for enhancing safe sexual behavior among college students in the context of universal higher education, as well as strengthening the self-protection of college students and providing practical advice for the development of sex education in China.