[GRAPHICS] A novel ionic siloxane hybrid electrolyte was fabricated by thermal polymerization of iodide-oligosiloxane resin. The nanosized iodide-oligosiloxane was synthesized by a simple sol-gel condensation of 3-iodopropyltrimethoxysilane and diphenylsilanediol. It is found that the composition and concentration of the oligosiloxane used in the electrolyte affect the performance of the dyesensitized solar cells (DSSCs). An optimized DSSC with the hybrid electrolyte using smaller molecular-sized oligosiloxane with a greater amount of iodide groups presented solar to electricity conversion efficiency of 5.2% at 1 sunlight (100 mW cm(-2)), which is comparable to that afforded by a liquid electrolyte.