Electrospun TiO2 nanofibers were employed to the quasi-solid state dye-sensitized solar cells with porous electrodes, which enhanced the penetration of viscous polymer gel electrolytes. The morphology of electrospun TiO2 fibers was affected by the electrospinning parameters such as the types of polymers, the concentration of polymer and titanium(IV) propoxide (TiP), the ratio of TiP/PVAc. The TiO2 fibers electrospun from poly( vinyl acetate) matrix formed the one-dimensionally aligned fibrillar morphology as an islands-in-a-sea structure. The new TiO2 electrodes demonstrated that the photocurrent generation with polymer gel electrolytes was over 90% of the performance in a dye-sensitized solar cell with liquid electrolytes.