The interaction between nitrilium derivatives of the closo-decaborate cluster [2-B10H9NCR]− (R=Et, t-Bu) with a number of aliphatic alcohols has been considered. The dependence between the type and composition of the final products and the structure of nitrilium derivatives and corresponding alcohols was studied. Compounds obtained were characterized by IR and NMR (1H, 11B, 13C) spectroscopy. The crystal structures of some derivatives of the closo-decaborate anion were determined by X-ray diffraction.