A novel polyblend electrolyte consisting of KI and I-2 dissolved in a blending polymer of polyvinyl pyrrolidone (PVP) and polyethylene glycol (PEG) was prepared. The formation of I-3(-) in the polymer electrolyte was confirmed by X-ray photoelectron spectroscopy (XPS) characterization. Due to the coordinating and plasticizing effect by PVP, the ionic conductivity of the polyblend electrolyte is enhanced. The highest ionic conductivity of 1.85 mS cm(-1) for the polyblend electrolyte was achieved by optimizing the compositions as 40 wt.% PVP + 60 wt.% PEG + 0.05 mmol g(-1) I-2 + 0.10 mmol g(-1) KI. Based on the polyblend electrolyte, a DSSC with fill factor of 0.59, short-circuit density of 9.77 mA cm(-2), open-circuit voltage of 698 mV and light-to-electricity conversion efficiency of 4.01% was obtained under AM 1.5 irradiation (100 mW cm(-2)). (c) 2007 Published by Elsevier Ltd.