This study investigated the relationship between plasma concentrations of beta-carotene and the alpha-tocopherol/lipid ratio, and smoking in 233 postpartum women, from July to November 2002, in the city of Joinville, Brazil. Thirty-seven percent (37%) of the women included in this study had low concentrations of alpha-tocopherol (< 11.63 micromol/L) and 61% of the women presented low concentrations of beta-carotene (< 0.39 micromol/L). Multivariate regression analysis investigated the relationship between smoking and the concentration of the vitamins, adjusting by confounding variables. The final regression model showed inverse associations between beta-carotene concentrations and smoking (p = 0.036), and beta-carotene concentrations and triglyceride levels (p = 0.021). There was an association between the plasma alpha-tocopherol/lipid ratio and per capita income (p = 0.003), but no association with smoking. We advise further studies to evaluate the impact of smoking and oxidative stress on the concentrations of these vitamins.