Solvate ionic liquids (ILs) are promising candidates for several applications due to their stability, high coulombic efficiency, and low volatility. In this work, we investigate the solvation of lithium-bistriflimide by different glycerol-derived triether solvents, using molecular dynamics simulations. Very strong interactions between Li+ and the solvent oxygen sites are found, leading to significant conformational changes in the solvent. By comparing the conformation of the neat solvents with their IL mixtures at different concentrations and temperatures, we find that the presence of Li+ induces a distinct crown-like structure in the solvent molecules. The Li+ cations and the surrounding solvent form a podand complex, which is stable even at elevated temperatures. These glycerol-derived solvents exhibit distinct interactions with Li+ cations which may be exploited in electrolytic applications or lithium recovery processes.