The performance of liquid chromatography–tandem mass spectrometry (LC–MS/MS) and extraction radioimmunoassay (RIA) to measure androgen concentrations was compared in 208 women with primary ovarian insufficiency, 200 patients with polycystic ovarian syndrome and 45 healthy controls. The precision, sensitivity and accuracy of the two methods for testosterone, androstenedione and dehydroepiandrosterone measurement were comparable. These results suggest that LC–MS/MS is a convenient alternative to RIA for measurement of androgen concentrations in women.