Objective: To evaluate the predictive value of maternal neutrophil-to-lymphocyte ratio (NLR) for spontaneous delivery within 24 hours in women with preterm premature rupture of membranes (PPROM). Study Design and setting: Retrospective cohort study in a single, university-affiliated tertiary medical center. Population: Women with PPROM at <33+6 weeks’ gestation planning vaginal delivery. Exclusions included cases of labor induction or cesarean delivery. Main outcome measure: Women who delivered spontaneously within 24 hours from rupture of membrane Methods: Maternal demographic and clinical data, including age, gestational age, body mass index, parity, and mode of conception, were collected. Women who delivered spontaneously within 24 hours of membrane rupture were compared to those who did not via univariate and multivariate Cox analyses. Results: Among 145,833 deliveries during the study period, 1,442 women (0.9%) presented with PPROM. After exclusions, 249 women were included, with 115 (46.2%) delivering spontaneously within 24 hours. Cox regression analysis identified NLR >10 (HR = 2.86, 95% CI 1.42–5.7, p = 0.003) and multiple gestation (HR = 5.87, 95% CI 2.57–13.45, p < 0.001) as independent risk factors for spontaneous delivery within 24 hours. Conclusion: An elevated maternal NLR is a promising predictor of spontaneous delivery within 24 hours in PPROM cases. These findings support the potential of NLR as a practical clinical tool for anticipating imminent preterm delivery, aiding in management decisions for this population. Funding: None.