A quasi-solid-state dye-sensitized solar cell employing a poly(ethylene oxide)-poly(vinylidene fluoride) (PEO-PVDF)/TiO2 gel electrolyte modified by various concentrations of water and ethanol is described. It is shown that the introduction of water and ethanol prevents the crystallization of the polymer matrix, and enhances the free I(-)/I(3)(-) concentration and the networks for ion transportation in the electrolyte, thus leading to an improvement in conductivity. A high energy conversion efficiency of about 5.8% is achieved by controlling the additive concentration in the electrolyte. Optimization of the additive-modified electrolyte performance has been obtained by studying the cross-linking behavior of water and ethanol with Fourier transform infrared (FTIR), differential scanning calorimetry (DSC) and viscosity measurements, and the electrical conduction behavior of the electrolyte with impedance spectra measurements.