In an attempt to evaluate the background levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), non-ortho, mono-ortho and indicator polychlorinated biphenyls (PCBs) in people living in an urban (Athens) and a rural (Kozani) area of Greece, blood serum and mother milk samples were analyzed. Analytical results are reported in this study. Statistically significantly differences were observed between regions, sexes and ages. Contamination levels in blood and human milk from Greece reported here are low compared to the previously reported dioxin data from other European countries and give no indication of particular health risk.