Thermal properties of the component materials are key issues in lithium ion batteries (LIBs). Si-based anodes are one of the most promising materials, but its thermal evolution have received much less attention than its electrochemical performance. In this article, the thermal behavior of various of Si material has been studied by differential scanning calorimetry (DSC). Three kinds of Si-particles, ranging from nano-to micro-sizes was subject to thermal analysis. It has been found that the thermal stability increases with the rise in particle-size. For the nanoparticles of 20 nm, both characteristic peaks of A and B regions in the heating process are stronger than the large-diameter particles. For three kinds of Si particles, the starting temperature of thermal reaction demonstrates a similar trend, gradually becoming lower with the increasing of the lithiation extent. At last, the ex situ XPS has also been conducted to explore the causes of surface state after temperature elevation. In A region, the heating decomposition of SEI with electrolyte, mainly consisting of a variety of esterification compounds, produces high content of lithium carbonate below 180 °C. When lithium in the inner phase of Si particles loses the protection of SEI film, the severe exothermic reaction occurred between lithium and the solvent species.