The molecular structures of the species crystallizing from solutions of alkoxytitanasilsesquioxanes in hydrocarbons upon reflux confirm the partial release of solvating alcohol. They feature, however, distinctly the formation of a dinuclear core with preserved hexacoordination for the metal atoms. The active titanium centers in the silica-titania epoxidation catalysts, lacking the sterically demanding ligands, are thus quite probably also hexacoordinated.