Polymer electrolytes were prepared with hyperbranched polyurethane, linear polyurethane as the host polymer, and lithium perchlorate (LiClO4) as the ion source. Fourier transform infrared spectra were used to analyze the bonding degree of Li+ with carbonyl and ether groups. Raman spectra were applied to analyze the aggregate degree of anion perchlorate ion (CLO4-). The spectra analysis indicated that the hyperbranched polyurethane could function as a "solvent" for the lithium salt. Also, the conductivity increased with increasing concentration of hyperbranched polymers in the host polymer.