A new unsymmetrical lithium salt containing C6H4O2 2−[dianion of 1,2-benzenediol] and C2O4 2−[dianion of oxalic acid], lithium [1,2-benzenediolato(2-)-O,O′ oxalato]borate (LBDOB), is synthesized and characterized. The thermal characteristics of it, lithium bis[1,2-benzenediolato(2-)-O,O′]borate (LBBB) and lithium bis(oxalate)borate (LiBOB) are examined by thermogravimetric (TG) analysis. The thermal decomposition in Ar begins at 250, 256, and 302°C for LBBB, LBDOB, and LBOB, respectively. The order of the stability toward oxidation of these organoborates is LBOB>LBDOB>LBBB, which is in the same order of the thermal stability. The cyclic voltammetry study shows that the LBDOB solution in PC is stable up to 3.7V vs. Li+/Li. They are soluble in common organic solvents. Ionic dissociation properties of LBDOB and its derivatives are examined by conductivity measurements in PC, PC+DME, EC+DME, PC+THF, EC+THF (molar ratio 1:1) solutions. The conductivity values of the 0.10moldm−3 LBDOB electrolyte in PC, PC+DME, EC+DME, PC+THF, EC+THF solutions are higher than those of LBBB, but lower than those of LBOB electrolytes.