Room-temperature-fused Li salt solvates that exhibit ionic liquid-like behaviour can be formed using particular combinations of multidentate glymes and lithium salts bearing weakly coordinating anions, and are now deemed a subset of ionic liquids, viz. solvate ionic liquids (SILs). Herein, we report redox-active glyme–Li salt molten solvates consisting of tetraethyleneglycol ethylmethyl ether (G4Et) and lithium iodide/triiodide, [Li(G4Et)]I and [Li(G4Et)]I₃. The coordination structure of the complex ions and the thermal, transport, and electrochemical properties of these molten Li salt solvates were investigated to diagnose whether they can be categorized as SILs. [Li(G4Et)]⁺ and I₃⁻ were found to remain stable as discrete ions and exist as well-dissociated forms in the liquid state, indicating that [Li(G4Et)]I₃ can be classified as a good SIL. This study also clarified that the I⁻ and I₃⁻ counter anions exhibit an electrochemical redox reaction in the highly concentrated molten Li salt solvates. The redox-active molten Li solvates were further studied as a highly concentrated catholyte for use in rechargeable semi-liquid lithium batteries. Although the cell constructed using [Li(G4Et)]I₃ failed to charge after the initial discharge step, the cell containing [Li(G4Et)]I demonstrates reversible charge–discharge behaviour with a high volumetric energy density of 180 W h L⁻¹ based on the catholyte volume.