OBJECTIVE: To evaluate the association among characteristics of primary health care center (PHCC) with hospitalizations for primary care sensitive conditions (PCSC) in Brazil. METHOD: In this study, a cross-sectional ecological study was performed. This study analyzed the 27 capitals of Brazil’s federative units. Data were aggregated from the following open access databases: National Program for Access and Quality Improvement in Primary Care, the Hospital Information System of Brazilian Unified Health System and Annual Population Census conducted by the Brazilian Institute of Geography and Statistics. Associations were estimated among characteristics of primary care with the number of three PCSC as the leading causes of hospitalization in children under-5 population in Brazil: asthma, diarrhea, and pneumonia. RESULTS: In general, PHCC showed limited structural adequacy (37.3%) for pediatric care in Brazil. The capitals in South and Southeast regions had the best structure whereas the North and Northeast had the worst. Fewer PCSC hospitalizations were significantly associated with PHCC which presented appropriate equipment (RR: 0.98; 95%CI: 0.97–0.99), structural conditions (RR: 0.98; 95%CI: 0.97–0.99), and signage/identification of professionals and facilities (RR: 0.98; 95%CI: 0.97–0.99). Higher PCSC hospitalizations were significantly associated with PHCC with more physicians (RR: 1.23, 95%CI: 1.02–1.48), it forms (RR: 1.01, 95%CI: 1.01–1.02), and more medications (RR: 1.02, 95%CI: 1.01–1.03). CONCLUSION: Infrastructural adequacy of PHCC was associated with less PCSC hospitalizations, while availability medical professional and medications were associated with higher PCSC hospitalizations.