Poly(ethylene glycol) containing terminal azide groups, i.e. PEG-N(3), was synthesized by reacting poly(ethylene glycol diglycidyl ether) (PEGDGE) with NaN(3), as confirmed by (1)H NMR and FT-IR spectroscopy. The resultant PEG-N(3) Was complexed with Lil or ionic liquid (1-methyl-3-propylimidazolium iodide, MPII) and then crosslinked under UV irradiation to enhance the mechanical properties of the electrolytes. The ionic conductivity of electrolytes with MPII reached 1.6 x 10(-5) S/cm at 25 degrees C, which is ten-fold higher than that of electrolytes with LI (1.5 x 10(-6) S/cm), due to different chain mobility. A worm-like morphology of the TiO(2) nanoporous layer was observed in the FE-SEM micrographs, which resulted from the interfacial contact between the TiO(2) nanoparticles and the electrolytes. Dye-sensitized solar cells (DSSCs) employing electrolytes with MPII and Lil exhibited an energy conversion efficiency at 100 mW/cm(2) of 1.6% and 0.8%, respectively. Solar cell performances were further improved by up to 4.2% with careful optimization. (C) 2009 Elsevier B.V. All rights reserved.