Poly(siloxanes-g-oligo(ethylene oxide)) with acrylate groups at the terminal position were prepared and examined for the solid polymer electrolyte (SPE) by curing them. Poly(ethylene glycol) dimethyl ether (PEGDME) was added as a plasticizer. Conductivity of the resulting polymer electrolytes was greatly enhanced with increasing amounts of low molecular weight PEGDME. Maximum conductivity was found to be 8×10−4 S/cm at 30°C with an [EO]/[Li] ratio of about 8. These electrolytes showed oxidation stability up to 4.95V against the lithium reference electrode. Reversible electrochemical plating/stripping of lithium was observed on the nickel electrode. The plating/stripping efficiency of lithium on nickel was measured to be about 53%.