Background: International organizations recommend initiating breastfeeding within the first hour of life and maintaining exclusive breastfeeding for the first 6 months. However, worldwide rates of exclusive breastfeeding for 6-month-old infants is far from meeting the goal proposed by the World Health Organization, which is to reach a minimum of 50% of infants. Education is one of the factors affecting the initiation and continuation of breastfeeding, and incidentally, it is also related to lower health literacy. This study explored the influence of health literacy on maintenance of exclusive breastfeeding at 6 months postpartum. Methods: A longitudinal multicenter study with 343 women were recruited between January 2019 and January 2020. The first questionnaire was held during the puerperium (24–48 h) with mothers practicing exclusive breastfeeding, with whom 6-month postpartum breastfeeding follow-up was performed. Socio-demographic, clinical and obstetric variables were collected. Breastfeeding efficiency was assessed using the LATCH breastfeeding assessment tool. The health literacy level was evaluated by the Newest Vital Sign screening tool. A multivariate logistic regression model was used to detect protective factors for early exclusive breastfeeding cessation. Results: One third of the women continued exclusive breastfeeding at 6 months postpartum. Approximately half the participants had a low or inadequate health literacy level. An adequate health literacy level, a high LATCH breastfeeding assessment tool score (>9 points) and being married were the protective factors against exclusive breastfeeding cessation at 6 months postpartum. Conclusion: Health literacy levels are closely related to maintaining exclusive breastfeeding and act as a protective factor against early cessation. A specific instrument is needed to measure the lack of “literacy in breastfeeding”, in order to verify the relationship between health literacy and maintenance of exclusive breastfeeding