Thermoelectrochemical cells (TECs) provide conspicuous advantages, including a high Seebeck coefficient (S-e), design flexibility, and low cost compared with conventional thermoelectric devices. Here, we investigated TECs employing Li metal electrodes (Li-TECs) and a series of glyme (CH3O[CH2CH2O]nCH(3), n = 1-4, nG) solvents with 0.5-3.0 M lithium-imide salts (lithium bis [fluorosulfonyl] imide, LiFSI, and lithium bis[trifluoromethane sulfonyl] imide, LiTFSI). The S-e value and power performance of Li-TECs markedly depend on the nature of glyme solvents and Li salt concentration. The dependency of S-e on the solvation structure of the Li-ions is examined via Raman measurements, and the internal resistance of Li-TECs is analyzed using electrochemical impedance spectroscopy. Notably, a Li-TEC with 1.0 M LiFSI 1G displays about two times higher power density and about eight times higher conversion efficiency than a conventional Cu-TEC utilizing aqueous electrolytes, which is ascribed to the high S-e value and low thermal conductivity of the former. In addition, for a Li-TEC with 1.0 M LiFSI 1G, the low-temperature performance is examined to assess its practical feasibility.