A new type of ionic-liquid-functionalized SiO2 (IL-SiO2) was synthesized to develop a microporous polymer electrolyte for quasi-solid-state dye-sensitized solar cells. The samples were characterized by H-1-NMR, Fourier transform infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, and X-ray diffraction. Moreover, the ionic conductivity of the electrolytes was measured by an electrochemical workstation. Nanostructured silica containing imidazolium iodide showed excellent compatibility with the organic solvent. The incorporation of the IL-SiO2 component into the polymer matrix improved the electrochemical behavior of the gel polymer electrolyte. A dye-sensitized solar cell with a gel polymer electrolyte yielded an open-circuit voltage of 0.662 V, a short-circuit current of 13.40 mA/cm(2), and a conversion efficiency of 4.01% at 1 sun illumination. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 121: 1566-1573, 2011