A novel dimethyl sulfoxide/1,3-dioxolane (DMSO/1,3-DO) based electrolyte is proposed for lithium/carbon fluorides (Li/CF) batteries to enhance the discharge voltage plateau and energy density. Conductivities of the electrolyte of 1 mol L-1 LiBF4/DMSO+1,3-DO with different volume ratios are not identical, which have a maximum of 14.85 mS cm(-1). From the tests of galvanostatic discharge, the discharge voltage plateau of the Li/CF. battery with an electrolyte of 1 mol L-1 LiBF4/DMSO+1,3-DO (5:5, v:v) can reach 2.69 V at 0.1 C, delivering a maximum discharge capacity of 831 mAh g-, and the highest energy density of 2196 Wh kg(-1). Compared to Li/CF batteries with an electrolyte of 1 mol LiBF4/PC +DME (5:5, v:v), the energy density of Li/CF. batteries with an electrolyte of 1 mol L-1 LiBF4/DMSO+1,3DO (5:5, v:v) has been improved more than 12%. With the help of XRD, SEM, TEM, EIS, FT-IR and GC-MS analysis, the results of this work suggest that DMS0/1,3-DO based electrolyte can significantly improve the discharge performance of Li/CF. batteries and keep a good electrochemical stability during discharge. The main reason for improvement of discharge performance is decreasing of both the overpotential of electrochemical polarization of CF. cathodes during discharge and the overpotential of ohmic polarization by increasing the ion conductivity of electrolyte. (C) 2015 Elsevier Ltd. All rights reserved.