The microstructures of carbon precursors significantly affect the electrochemical performance of Si/C composite anodes. However, the interaction between Si and carbon materials with different structures is still unclear. Pitch-based materials undergoing different thermal treatments are superior sources for synthesizing carbons with different structures. Herein, different types of mesophase pitch (domain, flow-domain and mosaic structure) obtained from controllable thermal condensation are utilized to prepare Si/C composite materials and the corresponding models are established through finite element simulation to explore the correlation between the lithium storage properties of Si/C composites and the structures of carbon materials. The results indicate that the flow-domain texture pitch P2 has a better ability to buffer the volume expansion of silicon particles for its highly ordered arrangement of carbon crystallites inside could disperse the swelling stress uniformly alongside the particle surface. The sample Si@P2 exhibits the highest capacity of 1328 mA h/g after 200 cycles at a current density of 0.1 A/g as well as the best rate performance and stability. While sample Si@P3 in which the mosaic texture pitch P3 composed of random orientation of crystallites undergoes the fastest capacity decay. These findings suggest that highly ordered carbon materials are more suitable for the synthesis of Si/C composite anodes and provide insights for understanding the interaction between carbon and silicon during the charging/discharging process.