Background: Despite the fact that tobacco use during pregnancy produces adverse perinatal effects, some women continue to smoke. Health literacy (HL) is essential for health outcomes in adults. However, little is known about HL in pregnant women or postpartum women. The study aimed to analyse the relationship between the degree of HL of women during the early puerperium and tobacco use during pregnancy. Methods: A multicentre, descriptive, cross-sectional study was carried out with women in the early puerperium in a region of eastern Spain, between November 2017 and May 2018. Their HL level was obtained using the Newest Vital Sign (NVS) tool. Multivariate logistic models were adjusted to estimate the magnitude of association with tobacco use in pregnancy. Odds ratios (OR) were estimated with a 95% confidence interval. Results: 193 were included in the total. 29.5% (57) of pregnant women smoked tobacco during pregnancy, with a smoking cessation rate of 70.1% (40) while pregnant. 42.0% (81) of pregnant women had inadequate or limited HL. A low level of HL was strongly associated with tobacco use, adjusted by catchment area and age of first pregnancy (LRT p < 0.001; ROC curve = 0.71, 95% CI: 0.64–0.79). Conclusion: A low HL is associated with tobacco consumption during pregnancy. Whether low HL reflects the wide constellation of already-known socioeconomic, political and commercial determinants of tobacco use, or whether incorporating HL support interventions strengthens tobacco cessation activities in pregnancy, warrants further research. Still, it should be considered as essential to understanding the health disparities related to its consumption.</jats:p>