The term 'silsesquioxane' refers to structures with an even number of silicon atoms (i.e. [RSiO 3/2 ] n with n = even integer) and extended network solids (i.e. [RSiO 3/2 ]) which can achieve the idealized empirical formula for silsesquioxanes, (RSiO 3/2 ) ? . In order to avoid confusion, it is often useful to distinguish between 'fully condensed' and 'incompletely condensed' silisesquioxane frameworks. A fully condensed silsesquioxane has an empirical formula of [RSiO 3/2 ] n , whereas an incompletely condensed silsesquioxane possesses reactive Si-OH groups. A host of heterosilsesquioxanes including main-group, transitionmetal and lanthanide metallasilsesquioxanes are also available via functionalization of incompletely condensed silsesquioxanes. Recent applications include soluble models for silica-supported catalysts, and precursors to hybrid inorganic/organic materials. 1-14 For these reasons metallasilsesquioxanes generated from the coordination of incompletely condensed silsesquioxanes to high-valent transition metals have emerged as useful solution-state models for silica-supported catalysts.15 A wide range of silsesquioxanes can be prepared via the hydrolytic condensation reactions of trifunctional organosilicon monomers, as presented in Scheme 1.Herein, using mass spectrometry, we present evidence on the generation and characterization of a selected group of silsesquioxanes in neat hexane or n-hexane/ethanol (i.e. 90:10, v/v). The results in this study indicate that atmospheric pressure chemical ionization (APCI) and turbo ionspray (TISP) mass spectrometry (MS) could be useful Scheme 1.