A VOC 4-sensor array was applied to the analysis of blood samples collected from healthy young men living in two known Italian contaminated areas, i.e. Land of Fires (LF) and Valley of Sacco River (VSR). Data processed by Multivariate data analysis (PCA and Discriminant Analysis) showed a distinguishing between the two areas. The preliminary results stimulate the research towards new analyzes and more extensive biomonitoring campaigns in these areas of interest for health protection.