The preparation of alkylene-, arylene-, or benzylene-bridged ditin hexachlorides in high yields from the reaction of the corresponding hexacyclohexylated compounds with tin tetrachloride is described. The tetragonal geometry of the tin atom of 1,4-bis(trichlorostannyl)butane in the solid state indicates that no intramolecular or intermolecular interaction involving either end of the molecule exists in this compound. The ditin hexachlorides were successfully transformed in the corresponding hexaalkynides, precursors of hybrid materials.