The unsaturated polyoxyethylene (PEO) was synthesized by copolymerization of ethylene oxide with allyl glycidyl ether in toluene using bimetallic-oxa-alkoxide as a catalyst. The effects of polymerization conditions on conversion and intrinsic viscosity of the copolymer were studied. The unsaturated copolymer was characterized with infrared spectra, H-1 NMR, and wide-angle X-ray diffraction. The relationship between crystallinity of the copolymers and conductivity of their LiClO4, complexes were investigated. The copolymer with similar to 65 wt % PEO content exhibits a room temperature conductivity of 1 x 10(-4) S cm(-1) at a molar ratio of EO/Li = 20. The unsaturated PEO was graft-copolymerized with styrene using 2,2＇-azobis(isobutyronitrile) as initiator in toluene, with grafting efficiency similar to 50%. The purified graft copolymer was characterized with infrared spectra, H-1 NMR, and wide-angle X-ray diffraction, and was shown to have good emulsifying properties and a phase-transfer catalytic property. LiClO4, complex of the graft copolymer with 70 wt % PEO content exhibits a room temperature conductivity approaching 1 x 10(-4) S cm(-1) at molar ratio of EO/Li = 20/1.