Adolescent Internet addiction is an important social issue entailing extensive use of Internet and smartphones and its side effects. This study identified relevant psychological factors that affect excessive Internet use (EIU) and excessive smartphone use (ESU) in adolescents using structural equation modeling (SEM). A sample of 714 individuals drawn from lists of middle school students in South Korea completed self-administered questionnaires, including Young’s Internet Addiction Test (Y-IAT), the Smartphone Addiction Scale (SAS), and various clinical and psychological scales measuring depression, anxiety, attention deficit/hyperactivity disorder (ADHD), aggression, expression of anger, and the behavioral inhibition system (BIS)/activation system (BAS). The final model, fitted using SEM, showed that both clinical characteristics, including ADHD symptoms, aggression, expression of anger, depression, and anxiety, and personality characteristics, represented by BIS/BAS, played important roles in the severity of EIU or ESU. In particular, affective components such as depression and anxiety were significantly associated with both EIU and ESU, whereas aggression, the expression of anger, and ADHD symptoms affected only EIU. Furthermore, the association between ESU and EIU was significant. Although personality characteristics measured by the BIS and BAS scores did not have direct effects on addiction, they were associated with clinical features and might be risk factors for addiction. The model revealed significant pathways from personality and clinical features to EIU and ESU in adolescents and informed our basic understanding of the meaningful predictors of these addictions and their direct and indirect influences.