In this paper, the synthesis of 1-hexyl-3-methylbenzimidazolium iodide (HMBI) and 1-hexyl-3-propylbenzimidazolium iodide (HPBI) was developed by quaternization reaction of 1-hexylbenzimidazole and alkyl iodide under solvent-free condition using Teflon-lined, stainless autoclaves. Their thermal properties were measured on the thermo gravimetric analysis and differential scanning calorimeter. The influence of HMBI, HPBI and 1-methyl-3-propylimidazolium iodide (MPII) on redox behavior of I(3)(-) and I(-) was investigated by cyclic voltammetry and electrochemical impedance spectroscopy. It was found that the resulting HMBI and HPBI had high purity and the reaction time was shortened to 3 h. The thermal stability of HMBI and HPBI was better than that of alkylimidazolium iodides, and HMBI and HPBI were prone to exhibit the supercooling phenomena. The DSCs with HMBI, HPBI and MPII gave photoelectric conversion efficiency of 5.49%, 5.34% and 5.54%, respectively. (c) 2010 Elsevier Ltd. All rights reserved.