The increased use of Internet in the last decade has led to problematic behavior that can affect people’s individual and social functioning, especially among teenagers. The aim of this study was to explore the relation among Problematic Internet Use (PIU), attachment styles, and perception of family functioning in adolescence. Two hundred and sixty-six Italian adolescents (Males = 57.1%; Mage = 16.01; SD = 0.90) were involved and asked to fill-in a self-report questionnaire. The results of correlation’s analysis highlighted that preoccupied and fearful attachment styles and the problem solving dimension were significantly and positively related to PIU. Whereas, as regards family functioning dimensions, the ability to establish clear and defined roles, a clear and empathic affective response, an affective involvement and a general family functioning appear to be in significant and negative association with PIU. In line with these results, it would be recommendable the development of family-focused prevention programs for all adolescents at risk of PIU before they develop a full Internet Addiction. Further research on this topic is needed to develop a specific, autonomous, and comprehensive diagnostic process for PIU to avoid conceptual and treatment overlap between PIU and other kinds of addictive behaviors.