The pharmacokinetics and metabolism of 1,4‐dioxane were determined in four healthy male volunteers exposed to 50 ppm dioxane vapor for 6 hr. Samples of blood and urine collected during and after the exposure were analyzed for dioxane and its metabolite β‐hydroxyethoxyacetic acid (HEAA) by gas chromatography‐mass spectrometry. A pharmacokinetic model with associated parameters was constructed to describe the fate of dioxane and HEAA in humans. The model was compared to a model constructed previously for dioxane in rats. This comparison facilitates assessment of the hazard to humans of dioxane exposure by extrapolation of toxicological information obtained in rats.