The purpose of this study is to research and develop solid polymer electrolyte(SPE) for Li secondary battery. We investigated the effects of lithium salts, plasticizer addition, temperature dependence of conductivity and electrochemical stability window of polyethylene oxide(PEO) electrolytes. PEO electrolyte completed with LiCIO$\_$4/ shows the better conductivity than the others. PEO-LiCIO$\_$4/ electrolyte, when EO/Li$^$+/ ratio is 8, showed adequate conductivity around room temperature. By adding propylene carbonate and ethylene carbonate to PEO-LiCIO$\_$4/ electrolyte, its conductivity was higher than that of PEO-LiCIO$\_$4/ without those. Also PEO$\_$8/LiCIO$\_$4/ electrolyte remains stable up to 4.5V vs. Li/Li.