BACKGROUND: Despite their importance in population health among children and adolescents, our understanding of how individual items mutually interact within and between pediatric health-related quality of life (HRQOL) and school social capital is limited. METHODS: We employed network analysis in a general population sample of 7759 children aged 9-15 years to explore the network structure of relations among pediatric HRQOL and school social capital items measured using validated scales. Furthermore, network centrality was examined to identify central items that had stronger and more direct connections with other items in the network than others. Network structure and overall strength of connectivity among items were compared between groups (by sex and age). RESULTS: Our analysis revealed that the item related to school/academic functioning and the item related to shared enjoyment among students had the highest strength centrality in the network of HRQOL and school social capital, respectively, underpinning their critical roles in pediatric HRQOL and school social capital. Additionally, the edge connecting "I trust my friends at school" and "trouble getting along with peers" had the strongest negative edge weight among ones connecting school social capital and pediatric HRQOL constructs. Network comparison test revealed stronger overall network connectivity in middle schoolers compared to elementary schoolers but no differences between male and female students. CONCLUSION: The network approach elucidated the complex relationship of mutually influencing items within and between pediatric HRQOL and school social capital. Addressing central items may promote children's perceived health and school social capital.