A new solid polymer electrolyte PEO20-LiTf-Urea1.5 was prepared by solution casting technique. The energy of frontier orbitals for the components of the electrolyte was predicted by quantum chemistry calculations, and TG stability and electrochemical features were measured. Urea exhibited a lower HOMO energy than PEO, implying its enhanced stability against electrochemical oxidation. Experimentally addition of urea increases the ionic conductivity, which guarantees conductivity requirement for lithium ion batteries. It also results in significant improved electrochemical stability with good thermal stability. Favorable lithium stripping/plating performance is yielded, and it confirms the good stability of the solid electrolyte interphase for the PEO20-LiTf-Urea1.5 system.