3 beta-Hydroxy-5-androsten-17-one (dehydroepiandrosterone) sulphate has been separated from an extract of human saliva by ion exchange gel chromatography and identified by high resolution gas chromatography-high resolution mass spectrometry of the tert-butyldimethylsilyl derivative of the neutral steroid obtained by enzymic hydrolysis. Quantitative analyses, employing 7,7-2H-dehydroepiandrosterone sulphate as the internal standard, have indicated concentrations in the saliva of young adult subjects to be generally in the range 0.9-5.7 nmol/l, though concentrations as high as 10.7 nmol/l have been observed.