Methyl phenyl bis-methoxydiethoxysilane (MPBMDS) was prepared and its effects were investigated as an additive in 1.0moldm−3 LiPF6-propylene carbonate (PC)/dimethyl carbonate (DMC) (1:1, v/v) electrolyte for lithium ion batteries. The electrochemical properties of the electrolyte with MPBMDS were characterized by discharge/charge tests, cyclic voltammetry, electrochemical impedance spectroscopy, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The addition of MPBMDS can effectively prevent the decomposition and the co-intercalation of PC. In addition, burning tests showed that the addition of 4–13wt.% MPBMDS to the bare PC-based electrolyte effectively reduces the flammability. This eco-friendly compound provides a new promising direction for the development of bi- or multi-functional additives for lithium ion batteries.