We demonstrate that solid-liquid nanocomposites derived from porous organic cages are effective lithium ion electrolytes at room temperature. A solid-liquid electrolyte nanocomposite (SLEN) fabricated from a LiTFSI/DME electrolyte system and a porous organic cage exhibits ionic conductivity on the order of 1 × 10-3 S cm-1. With an experimentally measured activation barrier of 0.16 eV, this composite is characterized as a superionic conductor. Furthermore, the SLEN displays excellent oxidative stability up to 4.7 V vs Li/Li+. This simple three-component system enables the rational design of electrolytes from tunable discrete molecular architectures.