A new method for the Synthesis of hyperbranched polymers involving the use of AB, macromonomers containing linear units have been investigated. Two types of novel hyperbranched polyurethanes have been synthesized by a one-pot approach. The structures of monomers and polymers were characterized by elemental analysis, H-1 NMR, C-13 NMR, Fourier transform infrared spectroscopy, gel permeation chromatography, and thermogravimetric analysis. The hyperbranched polymers have been proven to be extremely soluble in a wide range of solvents. Polymer electrolytes were prepared with hyperbranched polymer, linear polymer as the host, and lithium perchlorate (LiClO4) as the ion source. Analysis of the isotherm conductivity dependence of the ion concentration indicated that these hyperbranched polymers could function as a "solvent" for the lithium salt. The conductivity increased with the increasing concentration of hyperbranched polymers in the host polymer.