Quasi-solid state polymer electrolytes have been prepared from poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) as gelator for 1-ethyl-3-methylimidazolium based ionic liquids (with anions like trifluoromethanesulfonate [EMIM][TfO], bis(trifluoromethanesulfonyl)imide [EMIM][Tf2N]) and polyacrylonitrile (PAN) for gelation of 1-ethyl-3-methylimidazolium dicyanamide [EMIM][DCA] as well as I-/I-3(-) as the redox couple. All electrolytes exhibit high ionic conductivity in the range of 10(-3) S/cm. The effect of gelation, redox couple concentration, I-/I-3(-) ratio, choice of cations and additives on the ttiiodide diffusion and charge-transfer resistance of the platinum/electrolyte interface (R-ct) were studied. The apparent diffusion coefficient of triiodide ion (D(I-3(-))) at various iodide/triiodide ratios in liquid and gelified electrolytes has been calculated from measurements of the diffusion limited current (I-lim) in electrochemical cell resembling the set-up of a dye-sensitized solar cell. The charge-transfer resistance of the platinum/electrolyte interface as well as the capacitance of the electrical double layer (C-dl) have been calculated from impedance measurements. Electrolytes with reduced content of polymer (2.5 wt.%) were doped with Al2O3 particles of different sizes (50 nm, 300 nm, 1 mu m). The dispersion of the particles proceeds by speedy stirring of the hot electrolyte and the addition of PAN provides a homogeneous suspension. The addition of Al2O3 particles causes a slight increase of the triiodide diffusion constants. Furthermore the suggested enhancement of the charge transfer rate shows a dependence on the size of the particles. (c) 2006 Elsevier B.V. All rights reserved.