Lithium-cyclo-difluoromethane-1,1-bis(sulfonyl)imide (LiDMSI) was evaluated as an electrolyte additive in lithium-ion batteries for improved high voltage applications. Cycling the cathode at high potentials leads to the electrochemical oxidation of the salt to form a cathode electrolyte interphase (CEI) layer on the cathode surface. With the addition of 2 wt% of LiDMSI to the 1 M LiPF6 in 1 : 1 (by wt) EC : DEC electrolyte, the capacity retention and the Coulombic efficiency in LiNi1/3Co1/3Mn1/3O2/Li-half-cells as well as in LiNi1/3Co1/3Mn1/3O2/graphite-full-cells were improved. The cycling results point out the less over-potential and resistance at the cathode/electrolyte interface. These improvements are studied by SEM, EIS and XPS techniques.