The aim of undertaken long-term studies of the elemental composition of human serum, urine, and hair is to dene reference values of elements concentration. For this purpose the total reection X-ray uorescence method was applied to determination of several elements concentration in human serum, urine and hair (S, K, Ca, Fe, Cu, Zn, Br, P, Cr, and Rb in serum samples; Fe, Cu, Zn, Rb, Cr, Mn, and Sr in urine samples; S, K, Ca, Fe, Cu, Br, Zn, Cl, Ti, Cr, Mn, Ni, and Se in hair samples) in the range of concentration from ppb to several hundred ppm. The method of selection of the control group, the experimental setup and its calibration procedure are described. We also present sample preparation methods and procedure of measurements.