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 dye-sensitized 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.