Microsized silicon particles are desirable Si anodes because of their low price and abundant sources. However, it is challenging to achieve stable electrochemical performances using a traditional microsized silicon anode due to the poor electrical conductivity, serious volume expansion, and unstable solid electrolyte interface. Herein, a composite microsized Si anode is designed and synthesized by constructing a unique polymer, poly(hexaazatrinaphthalene) (PHATN), at a Si/C surface (PCSi). The Li+ transport mechanism of the PCSi is elucidated by using in situ characterization and theoretical simulation. During the lithiation of the PCSi anode, CN groups with high electron density in the PHATN first coordinate Li+ to form CNLi bonds on both sides of the PHATN molecule plane. Consequently, the original benzene rings in the PHATN become active centers to accept lithium and form stable Li‐rich PHATN coatings. PHATN molecules expand due to the change of molecular configuration during the consecutive lithiation process, which provides controllable space for the volume expansion of the Si particles. The PCSi composite anode exhibits a specific capacity of 1129.6 mAh g−1 after 500 cycles at 1 A g−1, and exhibits compelling rate performance, maintaining 417.9 mAh g−1 at 16.5 A g−1.