This study aims to evaluate maternal vaccine hesitancy and its associated factors. This is a cross-sectional study of a probabilistic sample of 450 mothers of children born in 2015, living in a Brazilian city, and who was, at the time of data collection, more than two years old. We used the tool proposed by the World Health Organization (10-item Vaccine Hesitancy Scale). To assess its structure, we performed, exploratory and confirmatory factor analyses. We performed linear regression models to evaluate the factors associated with vaccine hesitancy. The factor analysis showed two components for the vaccine hesitancy scale: lack of confidence in vaccines and risk perception of vaccines. High family income was associated with lower vaccine hesitancy (greater confidence in vaccines and lower risk perception of vaccines), while the presence of other children, regardless of birth order, in the family was associated with lower confidence in vaccines. A good rapport with health professionals, willingness to wait for the vaccination and the getting vaccinated through campaigns were associated with greater confidence in vaccines. The deliberate delay or decision not to vaccinate their children and previous experience with adverse reactions to the vaccine were associated with lower confidence in vaccines and greater risk perception of vaccines. Health care providers, especially nurses, play a relevant role to address vaccine hesitancy, guiding vaccination through a trustworthy rapport.