Introduction: Problematic internet use (PIU) is a psychopathology that includes multiple symptoms and psychological constructs. Because no studies have considered both network structures and clusters among individual symptoms in the context of PIU in a Korean adolescent population, this study aimed to investigate network structures and clustering in relation to PIU symptoms in adolescents. Methods: Overall, 73,238 adolescents were included. PIU severity was assessed using a self-rating scale comprising 20 items and 6 subscales, namely, the Internet Addiction Proneness Scale for Youth-Short Form; KS scale. Network structures and clusters among symptoms were analyzed using a Gaussian graphical model and exploratory graph analysis, respectively. Centrality of strength, closeness, and betweenness scores was also calculated. Results: Our study identified four clusters: disturbance in adaptive functioning, virtual interpersonal relationships, withdrawal, and tolerance. The symptom of confidence served as a node bridging the cluster of virtual interpersonal relationships and other clusters of withdrawal and disturbances of adaptive function. The symptom of craving served as a bridge between the clusters of withdrawal and tolerance with high betweenness centrality. Conclusion: This study identified network structures and clustering among PIU symptoms in adolescents and revealed that positive experiences derived from online interpersonal relationships were an important mechanism underlying PIU. These are novel insights concerning the interconnection among multiple symptoms and related clustering for the mechanism of adolescent PIU in terms of KS-scale PIU assessment.