Waterborne polyurethane synthesized from 4, 4＇-methylenebis( cyclohexyl isocyanate) (H12MDI), polyethylene glycol (PEG), and dimethyl propionic acid (DMPA) was employed as the matrix of polymer electrolytes. The influences of adding various of LiCF3SO3-PC on the conductivity of WPU-based electrolytes and the voltametric behavior at lithium/WPU interface are investigated by AC impedance analysis and cyclic voltammetry. The conductivities calculated from the results of AC impedance obey Arrhenius law with the activation energy of 10.33 kcal/mol, 9.82 kcal/mol, and 8.31 kcal/mol at 10 %, 30 %, and 50 % of LiCF3SO3-PC, respectively. On the basis of CV results, the lithium stripping/depositing processes were found to be facile at the lithium/WPU electrolyte interface. Comparisons of the conductivity as well as the voltametric behavior of H12MDI based WPU electrolytes and those of IPDI based WPU electrolytes are made to clarify the differences between two hard segments.