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Abstract A class of organic‐inorganic hybrid electrolyte with ion pair integrated network (X‐POSS‐IL‐LiTFSI) has been prepared by crosslinking of oligomeric octasilsesquioxanes grafted with imidazolium‐based ionic liquids for solid state lithium ion battery applications. X‐POSS‐IL‐LiTFSI is thermally stable and highly amorphous, and shows high ionic conductivities and excellent electrochemical stability. With further immobilization of a small fraction of ionic liquid, the ionic conductivity of X‐POSS‐IL‐LiTFSI has been significantly improved, e. g. 1.4×10−4 S/cm at ambinet temperature, to the level required by the practical battery applications, while maintaining the demensional integity. The coin cells of lithium batteries with the plasticized X‐POSS‐IL‐LiTFSI electrolytes exhibit high specific capacities at both ambient and elevated temperatures.more » « less