The "Triangle of Death" is an area of southern Italy highly polluted due to the presence of numerous illegal waste sites. To assess whether environmental contamination could produce an increased intake of harmful chemicals, we determined the serum levels of the 12 polychlorinated biphenyls (PCBs) indicated as "dioxin like" by the World Health Organization (WHO) in both maternal blood serum and umbilical cord blood serum of people residing in that area. The study was performed on 32 pregnant women and cord serum of their 32 newborn babies. Maternal serum concentrations ranged from 0.019 to 10.426 ng/mL (mean 1.590 ± 2.002 ng/mL), while umbilical serum concentrations ranged from 0.018 to 16.980 ng/mL (mean 1.858 ± 3.558 ng/mL). To normalize the toxic impact of the different congeners, the levels were expressed as WHO-TEQ, i.e., toxic equivalent concentrations. Total PCB concentrations (ΣPCBs WHO-TEQ 1998) were 0.297 TEQ-ng/mL in maternal serum and 0.663 TEQ-ng/mL in cord blood. These levels are significantly higher not only than those found in subjects resident in other areas but also in comparison to those reported in other published studies. This suggests that the exposure of both pregnant mothers and their fetuses to environmental pollution could produce a high intake of PCBs. The study may be important for the public health authorities to evaluate the level of exposure to environmental pollutants in human residents in the Triangle of Death.