Formaldehyde is a carcinogen to which humans are exposed daily, but few methods are available to quantify formaldehyde in biological samples. We developed a simple, sensitive and rapid technique for the quantification of formaldehyde in urine by derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine, using a headspace sampler coupled to a gas chromatograph equipped with an electron capture detector. The detection limit was 1.08 microg/L. The overall recovery of formaldehyde spiked in urine was 99%. The concentration of formaldehyde in urine obtained from healthy volunteers ranged from 56.85 to 144.57 microg/L. This method can be used successfully to measure formaldehyde in urine.