A new solid state electrolyte (SPE) containing self-complementary material was successfully synthesized.The presence of the highly interacted selfcomplementary sites induces the resulted solid state polymer electrolyte to exhibit more ordered structure and free-flowing ion conductive path and results in enhanced ionic conductivity.The new SPE exhibits half order higher ionic conductivity that the control SPE, indicating that the self-complementary material incorporated into SPE has the potential for the SPE application.A new concept of preparing SPEs is proposed.