Lithium bis(fluorosulfonyl)imide (LiFSI) has been studied as conducting salt for lithium-ion batteries, in terms of the physicochemical and electrochemical properties of the neat LiFSI salt and its nonaqueous liquid electrolytes. Our pure LiFSI salt shows a melting point at 145 °C, and is thermally stable up to 200 °C. It exhibits far superior stability towards hydrolysis than LiPF6. Among the various lithium salts studied at the concentration of 1.0 M (= mol dm−3) in a mixture of ethylene carbonate (EC)/ethyl methyl carbonate (EMC) (3:7, v/v), LiFSI shows the highest conductivity in the order of LiFSI > LiPF6 > Li[N(SO2CF3)2] (LiTFSI) > LiClO4 > LiBF4. The stability of Al in the high potential region (3.0–5.0 V vs. Li+/Li) has been confirmed for high purity LiFSI-based electrolytes using cyclic voltammetry, SEM morphology, and chronoamperometry, whereas Al corrosion indeed occurs in the LiFSI-based electrolytes tainted with trace amounts of LiCl (50 ppm). With high purity, LiFSI outperforms LiPF6 in both Li/LiCoO2 and graphite/LiCoO2 cells.