Multiple pregnancies are associated with an increased risk of obstetric complications as well as perinatal morbidity and mortality in developing countries because of the increased risk to both mother and baby. Therefore, the current study aimed to identify the maternal complications of multiple pregnancies among deliveries at Nangarhar University Teaching Hospital, Jalalabad, Afghanistan. A descriptive cross-sectional study was conducted on 442 mothers who gave multiple births at Nangarhar University Teaching Hospital, Jalalabad, Afghanistan, from March 2022 to September 2023 after obtaining ethical approval from the Institutional Review Committee (reference number: 10/02-15-2022). A non-probability-convenient sampling technique was used to select study participants. Data were collected using questionnaires from the hospital-based medical records of all participants. Those patients who were admitted to the obstetrics and gynecology ward for delivery with a clinical or ultrasound-confirmed diagnosis of multiple pregnancies after examination were included. The data were analyzed using the Statistical Package for Social Sciences (SPSS) version 26. A total of 22,409 births were recorded during this study at Nangarhar University Teaching Hospital; 442 were twin pregnancies, with a prevalence of 19/1000 births. The mean age of the study participants was 28.6 ± 5.3 years, while the mean age of gestation at the presentation was 36.5 ± 2 weeks. Among these, 425 (96.2%) births were twins, and 15 (3.4%) were triplets. The seven leading maternal complications of multiple pregnancies were postpartum hemorrhage (14.7%), preterm delivery (12.7%), preeclampsia (10.4%), antepartum hemorrhage (5.9%), urinary tract infection (5.9%), polyhydramnios (4.1%), and anemia (32.4%). The most common route of delivery was normal vaginal (78.5%). Multiple pregnancies are associated with a high risk of maternal complications, particularly postpartum hemorrhage, preterm labor, and preeclampsia; thus, maternal risks can be reduced by receiving adequate prenatal and postnatal care and early detection of maternal complications. Mothers carrying multiple pregnancies should receive immediate counseling regarding all the complications and should be kept under constant monitoring.