Poly(ether urethanes) obtained by the copolymerization of poly(ethylene glycol) (PEG) and lysine ethyl ester (LysOEt) are elastomeric materials that can be processed readily to form flexible, soft films. In view of these desirable physicomechanical properties, the potential use of these new materials as solid polymer electrolytes was explored. Solid polymer electrolytes were prepared with copolymers containing PEG blocks of different lengths and with different concentrations of lithium triflate (LiCF3SO3). Correlations between the length of the PEG block, the concentration of lithium triflate in the formulation, and the observed Li+ ion conductivity were investigated. Solid electrolyte formulations were characterized by differential scanning calorimetry for glass transition temperatures (T-g), melting points (T-m), and crystallinity. Ionic conductivity measurements were carried out on thin films of the polymer electrolytes that had been cast on a microelectrode assembly using conventional ac-impedance spectroscopy. These polymer electrolytes showed inherently high ionic conductivity at room temperature. The optimum concentration of lithium triflate was about 25-30% (w/w), resulting at room temperature in an ionic conductivity of about 10(-5) S cm(-1). For poly(PEG(2000)-LysOEt) containing 30% of LiCF3SO3, the activation energy was similar to 1.1 eV. Our results indicate that block copolymers of PEG and lysine ethyl ester are promising candidates for the development of polymeric, solvent-free electrolytes.