It is essential to consider the controllable microstructure of soft carbon and its enhancement effect on the electrochemical performance of silicon (Si) active materials. In this study, a series of Si@mesocarbon microbead (Si@MCMB) composites were prepared using mesophase pitch as the soft carbon source to coat nano-Si. The results showed that the ordered carbon layer stacking of soft carbon increased slightly with increasing heat treatment temperature in the range of 800–1400 °C. The Si@MCMB composites at higher temperature had a turbostratic carbon layer texture with rich porosity and smaller specific surface area, and had good cycle stability and high rate performance. These results highlighted that the co-existing structure of turbostratic carbon arrays with abundant porosity from soft carbon, provided the electron/ion transfer channels, underwent Si alloy volume change and enhanced the mechanical stability. Importantly, the relationship between the capacity retention rate of the Si@MCMB anodes and the microstructural characteristics (carbon layer and porosity) of soft carbon was established, which provided effective guidance for the design of high-performance silicon/carbon (Si/C) anode materials.