Gel-type polymer electrolytes based on the copolymer poly(ethylene oxide-co-epichlorohydrin) and the plasticizer gamma-butyrolactone (GBL) were optimized and applied in dye-sensitized solar cells. The plasticizer added to the electrolyte allowed the dissolution of a higher concentration of salt, reaching conductivity values close to 1 mS cm(-1) for the sample prepared with 30 wt% of LiI. Raman spectroscopy confirmed polyiodide formation in the electrolyte when the salt concentration exceeds 7.5 wt%, introducing a significant contribution of electronic conductivity in the electrolyte. The devices were characterized under AM 1.5 conditions and the I-V curves were fitted using a two diode equation. Increasing the concentration of LiI-I-2 accelerates dye cation regeneration as measured by transient absorption spectroscopy; however, it also contributes to an increase in the dark current of the cell by one order of magnitude. The best performance was achieved for the solar cell prepared with the electrolyte containing 20wt% of LiI, with efficiencies of 3.26% and 3.49% at 100 and 10 mW cm(-2) of irradiation, respectively. (C) 2008 Elsevier Ltd. All rights reserved.