Purpose Despite the health benefits of full breastfeeding for both infants and mothers, less than 50% of mothers in Germany practice this method for at least 4 months after childbirth. Because of the growing importance of health literacy to improve public health, we investigated the role of maternal health literacy in breastfeeding behavior. Methods We analyzed the data of 1172 mother–child dyads of the KUNO-Kids health study of the University Children’s and Maternity Hospital Regensburg. Maternal health literacy was assessed with the HLS-EU-Q47 questionnaire (sub-index health care) up to 48 h after childbirth. Outcome was analyzed 6 months after childbirth and categorized into full breastfeeding for less than 4 months or for at least 4 months. The association between breastfeeding and maternal health literacy was calculated with univariable and multivariable logistic regression analyses. Results 38.8% of mothers showed inadequate or limited health literacy. 75.9% of mothers had fully breastfed their child for at least 4 months. Univariable logistic regression analysis showed that health literacy and full breastfeeding for at least 4 months were not associated (OR = 0.995 CI 0.977–1.015, p  = 0.60). After adjusting for all potentially confounding variables with a significant association ( p  ≤ 0.05) on both health literacy and breastfeeding, the multivariable model showed no association between health literacy and breastfeeding (OR = 0.984 CI 0.963–1.007, p  = 0.170). Conclusion Surprisingly, we found no association between health literacy and breastfeeding behavior in our study. Therefore, future research with comparable measurements of health literacy and breastfeeding is required to validate this result and to identify reasons for early breastfeeding cessation.