Abstract: A new method of the derivatization of alcohols for their analysis by matrix-assisted laser desorption/ionization (MALDI) and surface-assisted laser desorption/ionization (SALDI) is proposed. The approach is based on the silylation of the analytes with bromomethylchlorodimethylsilane in the presence of tertiary amines to yield fixed-charge containing derivatives. The proposed method was tested using aliphatic alcohols, terpenols, and sterols. MALDI and SALDI mass spectra of all derivatives contain intense ion peaks corresponding to their cationic parts. © 2018, Pleiades Publishing, Inc.