A series of unsymmetrical zinc phthalocyanines bearing an anchoring carboxylic function linked to the phthalocyanine ring through different spacers were designed for dye-sensitised solar cells (DSSC). The modification of the spacer group allows not only a variable distance between the dye and the nanocrystalline TiO2, but also a distinct orientation of the phthalocyanine on the semiconductor surface. The photovoltaic data show that the nature of the spacer group plays a significant role in the electron injection from the photo-excited dye into the nanocrystalline TiO2 semiconductor, the recombination rates and the efficiency of the cells. The incident monochromatic photon-to-current conversion efficiency (IPCE) for phthalocyanines bearing an insulating spacer is as low as 9%, whereas for those with a conducting spacer an outstanding IPCE 80% was obtained.