Three different segmented thermoplastic polyurethanes (TPUs) were synthesized with 4,4 ' -methylenebis(phenyl isocyanate) as a hard segment and poly(ethylene glycol) (PEG) or poly(propylene glycol) (PPG) or an equal mixture of PEG and PPG with molecular 2000 as soft segments. The soft-segment component of TPU was changed to monitor modifications in chemical and physical properties among the three TPUs. Differential scanning calorimetry (DSC) and thermogravimetric analysis were used to monitor changes in thermal characteristics. Fourier transform infrared spectroscopy (FTIR) was employed to predict the interaction between the lithium cation and the hard or soft segment in the presence of added LiClO4. The deconvolution results of spectral bands associated with the N-H groups of these TPUs were used to obtain such information. Impedance spectroscopy was used to inspect the changes in the bulk conductivity of these TPUs caused by alteration of the soft-segment component. The conductivity changes were explained through combined DSC and FTIR results. The electrochemical stability of the TPU systems was studied by linear sweep voltammetry. The results showed that the copolymer system had better thermal and electrochemical stability than the other systems.