Polymeric nanocomposites of polyethylene glycol (PEG) with titanium oxide compound, PEG-Ti, have been prepared by sol-gel method from liquid PEG and titanium isopropoxide in acidic medium. Lithium salt (LiX) has been added into PEG-Ti to form PEG-Ti-LiX polymeric electrolytes. Electrochromic devices based on tungsten oxide thin films and PEG-Ti-LiX electrolyte may show excellent optical transmittance transient, however it depends on the type of lithium salt used during the sol-gel process. With LiI, the color change speed of the devices is very fast but they show a yellow color at bleaching state. The use of LiClO4 makes the devices totally transparent in visible region but the optical contrast is small. Possible molecular structure model of these polymeric electrolytes have been analyzed to explain the relation between electrochromic performance of tungsten oxide and electrolyte chemical composition.