A new unsymmetrical lithium salt containing F−, C6H4O2 2− [dianion of 1,2-benzenediol], lithium difluoro(1,2-benzene-diolato(2-)-o,o′)borate (LDFBDB) is synthesized and characterized. Its thermal decomposition in nitrogen begins at 170°C. The cyclic voltammetry study shows that the LDFBDB solution in propylene carbonate (PC) is stable up to 3.7V versus Li+/Li. It is soluble in common organic solvents. The ionic dissociation properties of LDFBDB are examined by conductivity measurements in PC, PC+ ethyl methyl carbonate (EMC), PC+dimethyl ether (DME), PC+ethylene carbonate (EC)+EMC solutions. The conductivity values of the 0.564moldm−3 LDFBDB electrolyte in PC+DME solution is 3.90mScm−1. All these properties of the new lithium salt including the thermal characteristics, electrochemical stabilities, solubilities, ionic dissociation properties are studied and compared with those of its derivatives, lithium difluoro(3-fluoro-1,2-benzene-diolato(2-)-o,o′)borate (FLDFBDB), lithium [3-fluoro-1,2-benzenediolato(2-)-o,o′ oxalato]borate (FLBDOB), and lithium bis(oxalate)borate (LBOB).