Thermally curable hybrid ionogel electrolytes consisting of epoxy-functionalized POSS, amine-terminated polypropylene glycol, and ionic liquid electrolyte, 1 M LiTFSI in BMPTFSI were fabricated to give ionic conducting epoxy networks with cubic inorganic star networks crosslinked with lithium ion dissociating polypropylene glycol linkers. Characterization of these hybrid ionogels revealed high ion conduction, exceptional thermal stability, and electrochemical stability. Lithium ion capacitors fabricated with these hybrid ionogels revealed exceptional performance on par with the neat liquid ionic liquid electrolyte, and far superior over ionogels fabricated with conventional organic crosslinkers, due to the mechanical robustness and lithium ion dissociative character imparted by the POSS and PPG functionalities.