A series of solid polymeric electrolytes has been prepared based on Polyvinyl Butyral (PVB) with different proportions of LiI salt. These polymeric electrolytes showed high ionic conductivity, which has been investigated as a function of the LiI concentration. The highest conductivity was seen at weight proportions 1:0.15 for PVB:LiI. An electrochromic device fabricated using this polymeric electrolyte showed good switching.