During our study a procedure of hair (62 samples) and teeth (38 samples) preparation for the XRF analysis was worked out. The samples were collected from the inhabitants of Katowice, Gliwice, Pyskowice and Tychy (Silesia, Poland). In hair samples S, Ca, Na, Mg, P, K, Mn, Fe, Cu, Zn, Sr, Pb content was determined and in teeth samples Ca, P, Na, Mg, Al, S, K, Fe, Ni, Cu, Zn, Sr, Pb content was determined. Conformity between the XRF and ICP results was obtained. Several correlations between the concentration of some elements and personal features (sex, age, smoking related) and environmental contamination were indicated. There were differences in the content of Al, Pb and Fe in women’s teeth and men’s teeth. A positive correlation between age and Mg, Fe, Cu, Sr and Pb content in teeth samples was noticed. Zn, S and Pb content depended on the level of pollution in the environment the samples came from. There were high levels of Zn and Pb concentration in teeth samples from smokers. In hair, positive correlations between the content of Ca, Fe and P and age were observed. Differences in Na, K and S content between women’s and men’s hair were noticed. Ca and Pb levels were different in samples obtained from different cities in Silesia. No correlation for Ba, Zn, Cu, Mn, Si was observed.