Five novel perylene molecules with different intramolecular charge-transfer (ICT) characters have been synthesized. The relation between the ICT character for different donating groups and the results for their electro- and photochemical properties as well as their performance in nanostructured dye-sensitized solar cells (nDSC) are reported. With the stronger donors, we obtain a shift of the lowest unoccupied molecular orbital (LUMO) to more negative potential versus normal hydrogen electrode (NHE) as well as an increase the charge separation in the dye upon excitation. Ab initio calculations were used to analyze the effects on orbital energies and electron distribution with the different donors. Incorporating the dyes in nDSCs, we see a drastical improvement in the performance for the more polar dyes. In particular, we find a much improved photovoltage because of higher LUMO levels, allowing conduction band tuning in the TiO2 as well as a contribution from the permanent dipoles in the dyes. The photocurrent improves remarkably with increasing ICT character of the dyes. The external quantum efficiency reached over 70%, and the overall solar-to-electrical energy conversion efficiency was improved to almost 4% for the dye with highest ICT character, which can be compared with devices with the standard N719 dye (Ru(dcbpy)(2)(NCS)(2)) showing 6% under similar conditions. The performance is a significant improvement compared to previous reports for perylenes and lifts the performance from modest to promising. Initial stability tests show that the dye with the highest performance was spectrally stable after more than 2000 h of irradiation in a solar-cell device.