The synthesis of soluble titanium(IV) phthalocyanines, axially substituted with phenylenevinylenes (PVs) (RxPcTiX), is described. The reaction of peripherally tetra- and octasubstituted (phthalocyaninato)titanium oxides (RxPcTiO) 1-3 with chelating PV-diols 4a-4c leads to the formation of axially substituted RxPcTiX 5-7. All compounds were characterized by IR, UV/Vis, MS, and H-1 NMR spectroscopy. Pcs 5-7 dissolved in dichloromethane are stable in the dark. The stability of solutions of 5-7 in sunlight depends on the nature of the peripheral substituents in the Pc ring and the chain length of the axial PV substituents. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).