Facebook is one of the most popular social network sites used by college students. Although some Western studies have started to explore the effect of Facebook use on individuals’ well-being, few empirical research has focused on these processes in Chinese college students. The primary aim of the study was to examine the association between Facebook use, loneliness, self-esteem, social support, and psychological well-being in a sample of Chinese college students. Participants were 680 Chinese college students aged 17–25 years across universities in Hong Kong. Path analyses indicated that Facebook use was associated with the well-being of Chinese college students in various ways. Using Facebook to connect to existing relationships was positively associated with social support. Results also indicated that social support and loneliness were mediators of the relationship between Facebook use and psychological well-being. The intensity of Facebook use was positively associated with loneliness, while using Facebook to connect to existing relationships had a positive association with individual well-being directly and indirectly. Implications of the results and further study directions are discussed.