Polymer electrolytes were prepared by blending high molecular weight poly(ethylene oxide) (PEO) and a series of novel quaternary ammonium iodides, the polysiloxanes with oligo(oxyethylene) side chains and quaternary ammonium groups. X-ray diffraction (XRD) measurements ensured relatively low crystallinity when the quaternary ammonium iodides were incorporated into the PEO host. The ionic conductivity of these complexes was improved with the addition of plasticizers. The improvement in the ionic conductivity was determined by the polarity, viscosity and amounts of plasticizers. A plasticized electrolyte containing the novel quaternary ammonium iodide was successfully used in fabricating a quasi-solid-state dye-sensitized solar cell for the first time. The fill factor and energy conversion efficiency of the cell were calculated to be 0.68 and 1.39%, respectively.