The prevalence of prenatal tobacco exposure remains high in many countries, particularly in southern Europe. The aims of this study were to estimate the prevalence of smoking among pregnant women in a southern Spanish city (Seville) and to identify the associated sociodemographic and obstetric characteristics. In a descriptive, cross-sectional study, a random sample of pregnant women who were scheduled to undergo a morphology scan at their public referral hospital in their 20th week of gestation were interviewed in person. At the start of pregnancy, 38.2% of the pregnant women were smokers. In the twentieth week, 19.1% continued to smoke, and the same percentage had quit. The prevalence of smoking in pregnant women was higher among those with a low level of education (60% among pregnant women with no studies and 30.4% in those with primary education) and among those who had had abortions (38.5%). Pregnant smokers with obesity were the least likely to have given up smoking during pregnancy. Women with a lower educational level should be a prime target for cross-sectoral interventions aimed at preventing prenatal tobacco exposure. Implementation of support measures for providing effective clinical advice in preconception and prenatal care regarding healthy lifestyles is particularly needed.