(1) Background: While the Robson Ten-Group Classification System (RTGCS) is widely used to assess and monitor caesarean section rates, its association with exclusive breastfeeding (EBF) outcomes at hospital discharge remains insufficiently explored. This study aimed to examine differences in EBF rates at hospital discharge across RTGCS groups among births attended at Hospital Universitario de la Ribera (Spain). (2) Methods: This retrospective observational study was conducted at a public hospital between 1 January 2010 and 31 December 2023. EBF at hospital discharge was analysed across Robson groups. Sociodemographic, obstetric, and neonatal variables were collected. A binomial logistic regression model was developed to identify predictors of EBF at discharge. Model fit was assessed using the Hosmer–Lemeshow goodness-of-fit test and Nagelkerke’s R2. (3) Results: The study analysed 23,081 births classified using the RTGCS, and 23,037 were included in the breastfeeding analysis. The overall EBF rate at discharge was 74.10%, with significant variation across Robson groups. Group 1 showed the highest EBF rate (78.339%) whereas Group 8 had the lowest (56.485%). Key factors positively associated with EBF included non-Spanish origin, nulliparity, cephalic presentation, singleton pregnancy, and term gestation. (4) Conclusions: Group 1 demonstrated the highest EBF rates, whereas Groups 8, 5, and 7 exhibited the lowest. These findings are essential for informing the development of targeted support strategies to improve breastfeeding outcomes in high-risk populations.