Internet addiction (IA) has become a major public health problem among college students. The aim of this study was to examine the relationship between self-identity confusion and IA and the mediating effects of psychological inflexibility and experiential avoidance (PI/EA) indicators in college students. A total of 500 college students (262 women and 238 men) were recruited. Their levels of self-identity were evaluated using the Self-Concept and Identity Measure. Their levels of PI/EA were examined using the Acceptance and Action Questionnaire-II. The severity of IA was assessed using the Chen Internet Addiction Scale. The relationships among self- identity, PI/EA, and IA were examined using structural equation modeling. The severity of self-identity confusion was positively associated with both the severity of PI/EA and the severity of IA. In addition, the severity of PI/EA indicators was positively associated with the severity of IA. These results demonstrated that the severity of self-identity confusion was related to the severity of IA, either directly or indirectly. The indirect relationship was mediated by the severity of PI/EA. Self-identity confusion and PI/EA should be taken into consideration by the community of professionals working on IA. Early detection and intervention of self-identity confusion and PI/EA should be the objectives for programs aiming to lower the risk of IA.