Early initiation of breastfeeding has been noted as one of the well-known and successful interventions that contributes to the reduction of early childhood mortality and morbidity. The Government of Benin has established multi-sectoral institutions and policies to increase the prevalence of early initiation of breastfeeding. However, there is little information on the prevalence and the determinants of early initiation of breastfeeding in Benin. This study therefore sought to examine the prevalence and determinants of early initiation of breastfeeding among women in Benin. This is a secondary data analysis of the 2017/2018 Benin demographic and health survey. The study included weighted sample of 7,223 women between the ages of 15 and 49. STATA was used for the data analysis. We used a multilevel logistic regression to investigate the factors of early breastfeeding initiation in Benin. To determine the significant relationships, the data were reported as odds ratios (ORs) with 95% confidence intervals (CIs) and p-value 0.05. The prevalence of early initiation of breastfeeding among mothers was 56.0%. Early initiation of breastfeeding was lower among employed women (aOR = 0.80, 95% CI = 0.69–0.94), women who had caesarean section (aOR = 0.21, 95% CI = 0.16–0.28), those exposed to mass media (aOR = 0.85, 95% CI = 0.75–0.96) and women who received assistance at birth from skilled worker (aOR = 0.57, 95% CI = 0.46–0.71). The findings of this study showed that four in ten children miss early initiation of breastfeeding in Benin. The findings, therefore, call for the need for policymakers to shape existing programs and consider new programs and policies to help improve early initiation of breastfeeding practices in Benin. It is, therefore, recommended that information, education and communication programs targeting mothers who are less likely to practice early initiation of breastfeeding be formulated, implemented, and monitored accordingly by the Ministry of Health.