This study investigated the association among internet addiction tendency, psychological capital, and well-being in upper elementary school students, and examined the mediating effect of psychological capital. A survey method was employed, and 258 valid questionnaires were collected. The research instruments included the Internet Usage Habits Scale, the Psychological Capital Scale, and the Well-Being Scale. Correlation analysis, structural equation modeling, and the PROCESS macro (Models 4 and 8) were used to analyze mediation and moderation effects. The results revealed that: (1) Internet addiction tendency was significantly negatively correlated with both psychological capital and well-being. Psychological capital was highly positively correlated with well-being. (2) Psychological capital partially mediated the relationship between internet addiction tendency and well-being, with self-efficacy showing the most significant mediating effect among its dimensions. (3) Gender and family structure showed moderating trends on the mediation pathways. Specifically, the psychological capital and well-being of female students and those from two-parent families were more susceptible to the influence of internet addiction tendency. In addition to discussing relevant research findings and limitations, this study also proposes, based on its results, that schools, families, and counseling agencies should plan and implement strategies to promote psychological capital. This approach aims to enhance students’ positive psychological resources and, consequently, mitigate the negative impact of internet addiction tendency.