This study demonstrates a sulfur-based compound, di(2,2,2-trifluoroethyl) sulfite (DTFES), as a new solid electrolyte interphase (SEI) forming additive on mesocarbon microbeads (MCMB). When placed in the electrolyte, it can dramatically enhance the performance of lithium-ion batteries (LIBs). The capacity loss was significantly decreased from 17.4% to 6.3% after 100 charge-discharge cycles due to the addition of DTFES. Differential capacity (dQ/dV) versus voltage (V) analysis showed that DTFES was decomposed in advance versus to electrolyte solvents. The effects of DTFES were characterized by charge-discharge testing, electrochemical impedance spectroscopy (EIS), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). These results indicate that the SEI film formed on MCMB by DTFES plays an important role in LIBs performance. Their subsequent reaction pathways are proposed in the paper.