The concentrations of fluorine (F), sodium (Na), magnesium (Mg), aluminum (Al), potassium (K), phosphorus (P), calcium (Ca), iron (Fe), nickel (Ni), zinc (Zn) and iodine (I) in the hair of 142 hydrofluoric acid (HF) exposed workers and 273 control subjects were analyzed by wavelength dispersive X-ray fluorescence spectrometry. Postshift urine and serum specimens were also collected for the determination of fluoride. To determine whether external contamination influences hair analysis, the control hair samples were kept in the work environment for one week. With the exception of lower K and Fe values, the levels of F and other elements in the hair of HF workers were higher than in the control subjects. The concentrations of F in hair and in postshift urine were in good correlation (r = 0.65). In the hair of HF workers F and Ca, F and Mg, F and P, F and Al were well correlated with each other (r greater than 0.6). F concentration in the hair increased after the sample was retained, however, it decreased to the reference value after washing. The levels of Ca, Mg and other elements did not change during the experiment.