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The objective of this study was to examine the experience of primary care center (PCC) users in Brazil, classified according to the quality of its structure, in relation to the aspects of accessibility, continuity, and acceptability. The source of information was the National Program to Improve Access and Quality of Primary Care in 2013-2014. A total of 109 919 interviewees in 24 055 PCCs comprised the sample. Results show that the structure of a PCC was associated with better indicators of accessibility (oral health and medicines) and continuity of care (patient navigation in the health system). No association was found between indicators of accessibility and the PCC structure.