Electrochemical characteristics of Li/FeS2 batteries having natural pyrite as cathode and liquid electrolytes have been studied at room temperature. The organic electrolytes used were 1M lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) in tetra(ethylene glycol) dimethyl ether (TEGDME) or a mixture of TEGDME and 1,3-dioxolane (DOX), and 1M LiPF6 in a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC). The pyrite powder and FeS2 cathode were characterized by SEM, EDS, XRD and charge/discharge cycling. The discharge capacities of Li/FeS2 cells with 1M LiTFSI dissolved in TEGDME were 772mAhg−1 at the 1st cycle and 313mAhg−1 at the 25th cycle at 0.1C. The cycling performance could be improved by using a mixture of TEGDME and DOX as the electrolyte. It was found that TEGDME contributed to high initial discharge capacity, whereas, DOX contributed to better stabilization of the performance. The first discharge capacities of Li/FeS2 cells showed a decreasing trend with higher current densities (615 and 534mAhg−1, respectively, at 0.5C and 1.0C). Li/FeS2 cells with the battery grade electrolyte 1M LiPF6 in EC/DMC had lower initial discharge capacity and cycling capability compared to the TEGDME system. The natural pyrite cathode with 1M LiTFSI dissolved in a mixture of TEGDME and DOX showed reasonably good first discharge capacity and overall cycling performance, suitable for application in room temperature lithium batteries.