Objective: To analyze the correlation between breastfeeding in the first hour of life with neonatal mortality rates. Methods: The present study used secondary data from 67 countries, obtained from the Demographic and Health Surveys. Initially, for data analysis, Spearman Correlation (95% CI) and Kernel graphical analysis were employed, followed by a Negative Binomial Poisson regression model, adjusted for potential confounders. Results: Breastfeeding within the first hour of life was negatively correlated with neonatal mortality (Spearman's Rho = −0.245, p = 0.046), and this correlation was stronger among countries with more than 29 neonatal deaths per 1000 newborns (Spearman's Rho = −0.327, p = 0.048). According to the statistical model, countries with the lowest breastfeeding tertiles had 24% higher neonatal mortality rates (Rate ratio = 1.24, 95% CI = 1.07-1.44, p < 0.05), even when adjusted for potential confounders. Conclusion: The protective effect of breastfeeding during the first hour of life on neonatal mortality in this ecological study is consistent with findings from previous observational studies, indicating the importance of adopting breastfeeding within the first hour as a routine neonatal care practice.