The solvent-dependent reassembling of a conventional dimeric [Ti-O-Ti] unit into a chainlike titanoxane under ionization conditions is reported. The titanoxane is the polymeric form of the tetrameric sequence [Ti=O-Ti-O-Ti-O=Ti] containing both the titanyl unit and the mu-oxo dimer, polymerization being achieved by a sharing of the oxygen atoms from the Schiff base ligand.