Prior studies have mainly focused on the psychological correlates of Internet addiction, but scant research has tested how actual interpersonal experience can influence people's tendency to spend an excessive amount of time online. The present research aimed to fill the research gap by investigating the potential relationship between ostracism and Internet usage as well as the mechanisms underlying such a linkage. Participants completed a series of well-validated measures assessing their ostracism experience in school, solitude seeking, self-control, and Internet addiction. The results established a significant positive association between ostracism and Internet addiction and demonstrated this relation was mediated by enhanced solitude seeking and impaired self-control. These findings advanced our current knowledge by showing that adverse interpersonal experiences in school can predict Internet addiction and by unveiling the underlying psychological mechanisms that can account for such a relation. They also highlight the importance of everyday interpersonal experiences in understanding people's behaviors in the cyberspace.