The extension of electrocatalytic reaction of I/I3 from counter electrode/gel electrolyte interface to gel electrolyte can significantly enhance the redox kinetics and therefore conversion efficiency of dye-sensitized solar cells. Microporous gel electrolyte from polypyrrole integrated poly(hydroxyethyl methacrylate/cetytrimethylammonium bromide) [PPy-integrated poly (HEMA/CTAB)] is successfully synthesized by in-situ polymerization of pyrrole monomers in three-dimensional framework of porous poly(HEMA/CTAB) matrix. An ionic conductivity of 12.72 mS cm−1 and activation energy of 8.65 kJ mol−1 are obtained from PPy-integrated poly(HEMA/CTAB) gel electrolyte. Tafel polarization and electrochemical impedance spectroscopy are employed to characterize the electrocatalytic behaviors of the gel electrolytes. The resultant quasi-solid-state dye-sensitized solar cell shows a light-to-electrical conversion efficiency of 6.68%. POLYM. ENG. SCI., 54:2531–2535, 2014. © 2013 Society of Plastics Engineers