Concentrations of Cd, Cr, Cu, Mn, Mo, Ni, Pb, Se, Tl and Zn were analyzed by ICP-MS in the scalp hair of male subjects from an urban area, three different quarters of Krakow, Poland, and from a rural area as control, which were assumed to differ in ambient pollution by metals. A questionnaire on personal data, nutritional habits, socioeconomic, occupation and health status was completed by the subjects. Significant differences (p < 0.05) were found in the levels of Cd, Cu, Mn and Ni between the locations. Using statistical methods of principal components analysis, the relationships were found between metals in the scalp hair as follows: Mn-Ni, Cr-Tl and Cd-Pb. Two separated clusters of smokers were revealed in the principal components, space suggesting other factors like environmental contamination could confound the values of parameters and relationships between them.