To define the relationship between fluoride (F) concentration in the serum, urine and hair of workers and the concentration of hydrofluoric acid (HF) in the work environment, pre- and postshift serum and urine samples of 142 HF exposed workers and 237 unexposed workers were examined. Hair specimens were also collected for the determination of F. To determine whether external contamination influences hair analysis, the control hair samples were kept in the work environment for one week. The pre-exposure levels in serum and urinary F in HF workers were higher (P < 0.01) than the control values. This suggests that F excretion from the body continues for at least 12 hours. The postshift serum and urinary F concentrations of these workers were significantly higher (P < 0.01) than the preshift concentrations. The levels of F in the hair of HF workers were also higher than in the control subjects. The concentrations of F in postshift serum and urine, and hair were in good correlation to each other. There was a linear relationship between mean serum and urinary F concentrations and HF concentration in the workplace. A mean F concentration of 82.3 micrograms/l in serum and 4 mg/l in urine with a lower fiducial limit (95%, P = 0.05) of 57.9 micrograms/l in serum and 2 mg in urine were estimated to correspond to an atmospheric HF concentration of 3 ppm, which is the maximum allowable concentration recommended by Japan Association of Industrial Health and also the threshold limit value suggested by American Conference of Governmental Industrial Hygienists.