We investigated whether older Korean women with prolonged breastfeeding duration have an increased risk of tooth loss, chewing difficulty, or undernutrition, as well as whether tooth loss and chewing difficulty mediate the association between breastfeeding duration and undernutrition risk. This study included 1666 women aged ≥65 years from the 2013–2015 Korea National Health and Nutrition Examination Survey who breastfed after delivery. The number of teeth and chewing ability were investigated based on the status of individual teeth and a self-report questionnaire, respectively. Dietary intake was estimated using the 24 h recall method. Compared with women who breastfed for 1–18 months, the odds ratios for tooth loss were 1.16 (95% confidence interval [CI] = 0.69–1.94), 1.79 (95% CI = 1.08–2.94), and 1.86 (95% CI = 1.16–2.97) among women who breastfed for 19–36, 37–72, and ≥73 months, respectively (p for trend = 0.004). Similar results were obtained for chewing difficulty and undernutrition. Furthermore, tooth loss and chewing difficulty partially mediated the association between breastfeeding duration and undernutrition risk. In conclusion, older Korean women who breastfed for longer periods are more likely to experience tooth loss, chewing difficulty, and undernutrition, which are particularly severe among women who breastfed for ≥37 months. The association between breastfeeding duration and undernutrition risk is mediated by tooth loss and chewing difficulty.