A highly ion conductive polymer was designed based on lithium N-methanesulfonylvinylsulfoneimide (LiMSVSI), a new vinyl monomer consisting of the smallest skeleton except the lithium bisulfonimide moieties. Its copolymer with poly(ethylene glycol) methyl ether acrylate exhibited good ionic conductivity in the range of 10 −4 -10 −5 S/cm.