This cross-sectional study evaluated the relationship between primary and secondary oral health care in Brazil. For this purpose, data from the National Program for Improving Access and Quality of Primary Care were used. Dentists from 12,403 oral health teams (OHTs) answered a structured questionnaire in 2012. The data were analyzed descriptively and by cluster analysis. Of the 12,387 (99.9%) OHTs that answered all the questions, 62.2% reported the existence of Dental Specialties Centers (DSCs) to which they could refer patients. The specialties with the highest frequencies were endodontics (68.4%), minor oral surgery (65.8%), periodontics (63.0%), radiology (46.8%), oral medicine (40.2%), orthodontics (20.5%) and implantology (6.2%). In all percentiles, the shortest wait time for secondary care was for radiology, followed by oral medicine and the other specialties. In the 50th percentile, the wait for endodontics, periodontics, minor oral surgery and orthodontics was 30 days, while for implantology, the wait was 60 days. Finally, in the 75th percentile, the wait for endodontics, orthodontics and implantology was 90 days or more. Two clusters, with different frequencies of OHT access to specialties, were identified. Cluster 1 (n = 7,913) included the OHTs with lower frequencies in all specialties except orthodontics and implantology compared with Cluster 2 (n = 4,474). Of the Brazilian regions, the South and Southeast regions had the highest frequencies for Cluster 2, with better rates for the relationship between primary and secondary care. This study suggests certain difficulties in the relationship between primary and secondary care in specific specialties in oral health, with a great number of OHTs with limited access to DSCs, in addition to different performance in terms of OHT access to DSCs across Brazilian regions.