The potential of preliminary silylation for the determination of numbers of hydroxyl groups in separate molecules of oligomeric silsesquioxanes by matrix-assisted laser desorption/ionisation mass spectrometry has been demonstrated for the first time Derivatisations allowing the introduction of trimethylsilyl, tert-butyldimethylsilyl and pentafLuorophenytdimethytsityl groups were tested. It was shown that more reliable structure elucidation of individual oligomers can be achieved knowing the number of hydroxyl groups thus determined.