Abstract: Silicon anodes are promising for use in lithium-ion batteries. However, their practical application is severely limited by their large volume expansion leading to irreversible material fracture and electrical disconnects. This study proposes a new top-down strategy for preparing microsize porous silicon and introduces polyacrylonitrile (PAN) for a nitrogen-doped carbon coating, which is designed to maintain the internal pore volume and lower the expansion of the anode during lithiation and delithiation. We then explore the effect of temperature on the evolution of the structure of PAN and the electrochemical behavior of the composite electrode. After treatment at 400 °C, the PAN coating retains a high nitrogen content of 11.35 at%, confirming the presence of C―N and C―O bonds that improve the ionic-electronic transport properties. This treatment not only results in a more intact carbon layer structure, but also introduces carbon defects, and produces a material that has remarkable stable cycling even at high rates. When cycled at 4 A g⁻¹, the anode had a specific capacity of 857.6 mAh g⁻¹ even after 200 cycles, demonstrating great potential for high-capacity energy storage applications.