The role of ethylene sulfite used either alone or in combination with VC in LiNi1/3Mn1/3Co1/3O2 (NMC)/graphite pouch cells was studied by correlating data from differential capacity (dQ/dV) analysis, gas chromatography/mass spectroscopy (GC-MS), theoretical calculations, ultrahigh precision coulometry, storage experiments and X-ray photoelectron spectroscopy. For cells containing VC alone, the electrochemical performance and gas production were greatly improved, compared to cells without VC, due to the formation of more stable and protective SEI films at both electrode surfaces by a polymer of VC. For cells with ES alone, a vigorous reactivity was observed due to preferential reduction that also generated large amounts of gas during formation. The dramatic decrease in electrochemical performance as well as the continuous production of gas during cycling in cells with ES was explained by the formation of a very thin and ineffective SEI film at the NMC surface. The suppression of the vigorous reaction of ES in cells with both ES and VC occurred because the solvation energy of Li(+) by VC is smaller than that of EC so VC is reduced first during formation. During charge-discharge cycling, a slow consumption of ES occurred and different sulfur species were observed on the electrodes when VC was combined with ES. SEI film formation processes and SEI composition were therefore dominated by VC and the electrochemical performance of cells with both VC and ES were similar compared to those of cells with VC alone.