A new solvent-free solid polymer electrolyte (SPE) films could be fabricated through bulk copolymerization process of amphiphilic urethane acrylate nonionomer (UAN). Amphiphilic UAN chain having polypropylene oxide-based hydrophobic segment and polyethylene oxidebased hydrophilic segment can not only dissolve lithium salt by complex formation with lithium cations but also be copolymerized with various monomers to form microphaseseparated polymeric matrix. Unlike conventional SPE systems showing higher conductivity with polar polymers and polar solvents, our SPE films prepared by copolymerization of UAN and hydrophobic monomers exhibited relatively higher conductivity. Dissolving lithium salts in UAN/hydrophobic monomer mixtures caused hydrophilic/hydrophobic microphase separation, which was more favorable for ionic conduction of lithium ions, resulting in the higher ionic conductivity than the SPE films fabricated using UAN/hydrophobic monomer mixture. This microphase-separated structure of SPE films could be also confirmed by transmission electron microscope (TEM) images. Ionic conductivity of our SPE films could be also improved by dispersing clay minerals within SPE films. Three types of clay having different surface properties were used to fabricate clay/SPE nanocomposite films. Ionic conductivity of nanocomposite films depended on dispersibliity of clay nanoparticles with a SPE film, which was confirmed by measuring X-ray diffraction and TEM.