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As an attractive candidate for anode materials, silicon has attracted extensive attention. The instability of electrode/electrolyte interphase due to the inherent volume variation upon (de)lithiation is one of the major factors that limit the commercialization of Si materials. The in-depth understanding of the interface reaction of Si is helpful to modify the interface properties of Si, and further improve the electrochemical performance. This review summarizes the research on the interface reaction mechanism of Si during (de)lithiation process, including Li-Si alloying process, the reactions of primary oxide layer and the formation of passivation film on the Si surface. Moreover, the effect of the three processes on the Si electrochemical performance are also discussed.