The low temperature behaviors of Li/TEGDME/S cell was examined using discharge curves, SEM and impedance spectra. The first discharge capacity of Li/S cell with tetra(ethylene glycol) dimethyl ether (TEGDME) electrolyte was 1303mAhg−1-sulfur at 20°C, but 357mAhg−1-sulfur at low temperature of −10°C. The low temperature discharge characteristic is improved by adding 1,3-dioxolane (DOXL) and methylacetate (MA) to TEGDME electrolyte. The optimum composition of mixed electrolyte is MA–DOXL–TEGDME (5:47.5:47:5, v/v). The Li/S cell using the optimum electrolyte has the first discharge capacity of 994 and 1342mAhg−1-S at −10 and 20°C, respectively.