A quasi-solid-state dye-sensitized nanocrystalline porous TiO2 film solar cell was fabricated using a novel gel network polymer electrolyte based on polysiloxanes with both polyethylene oxide internal plasticized side chains and quaternary ammonium groups. The cell exhibited better photoelectrical conversion performance under 60 mW/cm2 irradiation. The short photocurrent (Isc) of 5.0 mA/cm2 and open voltage (Voc) of 0.68 V were achieved, and the energy conversion efficiency (η) and fill factor (ff) were 3.4% and 0.60, respectively.