Due to the tendency of polychlorinated biphenyls (PCB) to accumulate in matrixes with high lipid content, the contamination of the breast milk with these compounds is a serious issue, mainly to the newborn. In this study, milk samples were collected from breastfeeding mothers belonging to 4 Brazilian regions (south, southeast, northeast and north). Twelve PCB were analyzed by HS-SPME-GC-ECD and the corresponding peak areas were correlated to the answers to a questionnaire of general habits, breastfeeding and characteristics of the living places. To realize this exploratory analyze, self-organizing maps generated applying Kohonen neural network were applied. It was possible to verify the occurrence of different PCB congeners in the breast milk relating to the region of the Brazil that the breastfeeding lives, the proximity to an industry, the proximity to a contaminated river or sea, the type of milk (colostrum, foremilk and hindmilk) and the number of past pregnancies.