Hydrophobic poly(hydroxyethyl methacrylate/glycerin) [poly(HEMA/GR)] gel with a three-dimensional (3D) framework was successfully fabricated and employed to integrate with polyaniline (PANi). The resultant poly(HEMA/GR)/PANi gel electrolyte exhibited interconnective porous structure for holding I-/I-3(-), giving a similar conduction mechanism and ionic conductivity to that of liquid system but a much enhanced retention of I-/I-3(-) redox couple. Fourier transform infrared spectroscopy, X-ray diffraction patterns, cyclic voltammograms as well as electrochemical impedance spectroscopy were employed to evaluate the molecular structure, crystallinity, and the electrochemical behaviors, showing that the combination of PANi with poly(HEMA/GR) caused a lower charge-transfer resistance and higher electrocatalytic activity for the I-/I-3(-) redox reaction in the gel electrolyte. An efficiency of 6.63% was recorded from the quasi-solid-state DSSC assembled with the poly(HEMA/GR)/PANi gel electrolyte at 100 mW cm(-2). (C) 2014 Elsevier B.V. All rights reserved.