The microwave pyrolysis of biomass and the directional design of biochar structure are examined in this study by exploring the internal connection between energy conversion and biochar structure evolution. Through the optimization of process parameters (microwave power and sample volume), the average utilization efficiency of microwave energy increased from 11.96% to 32.84%, and the specific surface area of the biochar increased from 453.89 m²/g to 638.82 m²/g. According to the simulation results of the COMSOL Multiphysics software, the distribution of the temperature field was closely related to the evolution of the microwave electric field intensity. The local high temperature areas (hotspots) were primarily located in the center of the biochar, and the temperature distribution gradually decreased from the inside to the outside. The hotspots contributed to the promotion of the conversion of amorphous carbon to graphite carbon. Meanwhile, the graphite carbon with a stronger microwave absorption capacity formed a local hotspot and promoted the growth of the pore structure. The rich pore structure of the biochar facilitated the multiple reflection of microwave energy and prolonged the microwave residence time. Graphite carbon can absorb microwave energy and convert it into heat energy to improve the utilization efficiency of microwave energy. This paper combined the experimental and simulation results to reveal the heat transfer mechanism in the microwave pyrolysis process, which provided a new perspective for the directional reduction of microwave pyrolysis energy consumption and the optimization of the microstructure of biochar.