AbstractA new, highly efficient and very simple method for the synthesis of pure octahedral methylsilsesquioxanes (CH3SiO3/2)8, from cyclic 2,4,6,8-tetraalkoxy- 2,4,6,8-tetramethylsiloxane, was developed. We have found that T8Me can be synthesized from a mixture of alkoxymethylcyclosiloxane isomers in the hydrolytic condensation process, utilizing an ionic catalyst - tetrabutylammonium fluoride (TBAF). The reaction was carried out under very mild conditions, at room temperature, in a variety of solvents of different polarity. A substantial solvent effect was observed. THF helped in the formation of pure T8Me, whereas in other solvents mixtures of T8Me and poly(methylsilsesquioxanes) (PMQS) of substantial degree of regularity, were obtained.