Methyl tetrafluoro-2-(methoxy) propionate (MTFMP) was evaluated as co-solvent for PC-based electrolytes in combination with graphite electrodes. Already 10wt% (5.6mol%) of MTFMP in PC were sufficient to form an effective and stable SEI on graphite as confirmed by battery tests. In the first cycle, the formation of an effective SEI via the decomposition of MTFMP was observed before PC co-intercalation thus preventing the subsequent exfoliation of the graphite. The stability of this SEI was verified by long term cycling tests, which showed that the capacity loss of the graphite-based cell was only 1.3% after 300 cycles at 1C. The electrolyte, 1M LiPF6 in PC:MTFMP (9:1wt%), showed also a good rate capability up to 5C on graphite. Therefore, MTFMP can be considered as a new, very promising co-solvent for PC-based electrolytes for use in lithium-ion batteries with graphite anodes.