Comparative data on the potential impact of various forms of labor analgesia on the mode of delivery and neonatal complications in vaginal deliveries of singleton breech and twin fetuses are lacking. The present study aimed to determine the associations between type of labor analgesia (epidural analgesia (EA) vs. remifentanil patient-controlled analgesia (PCA)) and intrapartum cesarean sections (CS), and maternal and neonatal adverse outcomes in breech and twin vaginal births. A retrospective analysis of planned vaginal breech and twin deliveries at the Department of Perinatology, University Medical Centre Ljubljana, was performed for the period 2013–2021, using data obtained from the Slovenian National Perinatal Information System. The pre-specified outcomes studied were the rates of CS in labor, postpartum hemorrhage, obstetric anal sphincter injury (OASI), an Apgar score of <7 at 5 min after birth, birth asphyxia, and neonatal intensive care admission. A total of 371 deliveries were analyzed, including 127 term breech and 244 twin births. There were no statistically significant nor clinically relevant differences between the EA and remifentanil-PCA groups in any of the outcomes studied. Our findings suggest that both EA and remifentanil-PCA are safe and comparable in terms of labor outcomes in singleton breech and twin deliveries.