Abstract Two novel amphiphilic zinc phthalocyanines (TAZnPc and ASZnPc) have been synthesized. It has been shown that they form stable monolayers on a nanometer-sized colloidal TiO 2 subphase and are suitable for the fabrication of alternating zinc phthalocyanine-titanium oxide multilayers via the Langmuir–Blodgett method. Surface pressure-area isotherm and absorption spectroscopic studies show that uniform TAZnPc (ASZnPc)–TiO 2 alternating multilayers are formed. It has been found that the TAZnPc molecules lie almost flat on the substrate surface, while ASZnPc molecules are oriented nearly perpendicular to the substrate surface. Transparent SnO 2 electrodes coated with alternating ASZnPc–TiO 2 multilayers were found to exhibit a higher photovoltage response than TAZnPc–TiO 2 coated electrodes. This demonstrates that the molecular arrangement of the zinc phthalocyanine moiety in the multilayers has an important influence on the photovoltaic properties of the sensitized SnO 2 electrode.