Increasing the number of infants exclusively breastfeeding on discharge from the hospital after birth is a key goal of breastfeeding policy in New South Wales (NSW), Australia. Despite consistent efforts, exclusive breastfeeding on discharge rates have declined over the past decade. Using pooled data from the New South Wales Perinatal Data Collection from 2011 to 2020, we examined the association between antenatal care (ANC) and exclusive breastfeeding at discharge from birth admission outcomes for mother–baby dyads in Southern New South Wales Local Health District (SNSWLHD). Our study confirmed that exclusive breastfeeding rates in SNSWLHD have declined over the past decade, providing local evidence to support action. Late entry to ANC and a failure to attend the recommended number of ANC visits were important predictors of a lower rate of exclusive breastfeeding on discharge. Improving accessibility to ANC visits for rural and regional mothers has potential to positively impact breastfeeding rates in SNSWLHD. We suggest that wider implementation of caseload midwifery models may have a positive impact on breastfeeding outcomes in the region for all mother–baby dyads, but particularly for Aboriginal mothers and infants, younger mothers and mothers experiencing disadvantage.