The effect of lithium salts such as LiPF6, LiBF4, LiCF3SO3 and LiN(CF3SO2)2 (LiTFSI) in tetra(ethylene glycol) dimethyl ether (TEGDME) electrolyte on the ionic conductivity, interfacial resistance and discharge properties of Li/pyrite cell at room temperature was studied. The electrolytes had good ionic conductivity at room temperature in the range 0.61 to 1.86 × 10-3 S/. The discharge capacities of Li/pyrite cells with 1M LiPF6 and LiBF4 in TEGDME were lower compared to those of the other two non-HF containing salts. The best cycle performance was exhibited by LiTFSI in TEGDME electrolyte, with a discharge capacity of 438 mAhg-1 after 20 cycles, which is ~49% of FeS2 theoretical capacity (894 mAhg-1). The good performance of LiTFSI-TEGDME electrolyte resulted mainly from its low interfacial resistance in Li/FeS2 cells, which showed a decreasing trend with cycling.