Vinyl ethylene sulfite (VES) is studied as a new additive in propylene carbonate (PC)-based electrolyte for lithium ion batteries. The electrochemical results show that the artificial graphite material exhibits excellent electrochemical performance in a PC-based electrolyte with the addition of the proper amount of VES. According to our spectroscopic results, VES is reduced to ROSO2Li (R=C4H6), Li2SO3 and butadiene (C4H6) through an electrochemical process which precedes the decomposition of PC. Furthermore, some of the Li2SO3 could be further reduced to Li2S and Li2O. All of these products are proven to be components of the solid electrolyte interface (SEI) layer.