Atomic-layer-deposited TiO2 recombination blocking layers were prepared on indium tin oxide-poly(ethylene terephthalate) (ITO-PET) photoelectrode substrates for dye solar cells and were examined using several electrochemical methods. The blocking layers increased the open-circuit voltage at low light intensities. At high light intensities, a decrease in the fill factor (FF) due to the additional resistance of the current transport through the layer was more significant than the positive effect by the reduced recombination. The decrease in the FF was reduced by a thermal treatment that made the blocking layer more conductive due to a structural change from an amorphous to a crystalline form. Therefore, thinner blocking layers of this type are required for plastic cells prepared at low temperature than for conventional glass dye solar cells made with temperature processing.