A new unsymmetrical lithium salt containing F−, C6O2F4 2− [dianion of tetrafluoro-1,2-benzenediol], lithium difluoro[tetrafluoro-1,2-benzenediolato(2-)-O,O′]borate (4FLDFBDB) is synthesized and characterized. The thermal characteristics of it, and its derivatives, lithium difluoro[3-fluoro-1,2-benzene-diolato(2-)-O,O′]borate (FLDFBDB), and lithium difluoro[1,2-benzene-diolato(2-)-O,O′]borate (LDFBDB) are examined by thermogravimetric analysis (TG). The thermal decomposition in air begins at 170°C, 185°C, and 230°C for 4FLDFBDB, FLDFBDB, and LDFBDB respectively. The order of the stability toward oxidation of these organoborates is 4FLDFBDB>FLDFBDB>LDFBDB. The cyclic voltammetry study shows that the 4FLDFBDB solution in propylene carbonate (PC) is stable up to 4.2V versus Li+/Li. They are soluble in common organic solvents. Ionic dissociation properties of 4FLDFBDB and its derivatives are examined by conductivity measurements in PC, PC+ethyl methyl carbonate (EMC), PC+dimethyl ether (DME), PC+ethylene carbonate (EC)+EMC. The conductivity values of the 0.10moldm−3 4FLDFBDB electrolyte in these solutions are higher than those of FLDFBDB and LDFBDB electrolytes.