The aim of this study was to characterize the placental transfer of some environmental pollutants, and to explore the possibility of quantitatively predicting in utero exposure to these contaminants from concentrations assessed in maternal blood. Levels of toxic substances such as pesticides (p,p’-DDE, β-HCH, and HCB), polychlorinated biphenyls (PCBs), perfluorooctane sulfonate (PFOS), and perfluorooctanoic acid (PFOA) were determined in serum samples of 38 pregnant women living in Rome and in samples of cord blood from their respective newborns. The study was carried out in the years 2008–2009. PCB mean concentrations in maternal serum and cord serum ranged from 0.058 to 0.30, and from 0.018 to 0.064 ng/g·fw respectively. Arithmetic means of PFOS and PFOA concentrations in mothers and newborns were 3.2 and 1.4 ng/g·fw, and 2.9 and 1.6 ng/g·fw. A strong correlation was observed between concentrations in the maternal and the foetal compartment for PFOS (Spearman r = 0.74, p < 0.001), PFOA (Spearman r = 0.70, p < 0.001), PCB 153 (Spearman r = 0.60, p < 0.001), HCB (Spearman r = 0.68, p < 0.001), PCB 180 (Spearman r = 0.55, p = 0.0012), and p,p’-DDE (Spearman r = 0.53, p = 0.0099). A weak correlation (p < 0.1) was observed for PCBs 118 and 138.