Lithium bis(oxalato)borate (LiBOB) is a promising salt for lithium ion batteries. However, before applying in lithium ion batteries, it is necessary to prepare high purity LiBOB with a simple method, and find more appropriate solvent systems to exert the perfect electrochemical performance of LiBOB. In this paper, LiBOB is synthesized by the compressing dry granulation method, with the yield of 97%. Moreover, the electrochemical performances of LiBOB-sulfolane (SL)/diethyl carbonate (DEC) electrolyte are investigated. It shows high oxidation potentials (>5.3V) and satisfactory conductivities, also the temperature dependence of the conductivity is well in accord with the Vogel–Tamman–Fulcher (VTF) behavior. When used in Li/MCMB (mesophase carbon microbeads) cells, this novel electrolyte exhibits not only excellent film-forming characteristics, but also low impedances of the interface films. When used in LiFePO4/Li cells, compared to the cell with the electrolyte system of LiBOB-EC/DEC electrolyte, LiBOB-SL/DEC electrolyte exhibit several advantages, such as more stable cycle performance, and higher discharge voltage plateau (>3.35V).