Abstract: Bioderived carbon materials have garnered considerable interest in the fields of microwave absorption and shielding due to their reproducibility and environmental friendliness. In this study, KOH was evenly distributed on biomass Tremella using the swelling induction method, leading to the preparation of a three-dimensional network-structured hierarchical porous carbon (HPC) through carbonization. The achieved microwave absorption intensity is robust at −47.34 dB with a thin thickness of 2.1 mm. Notably, the widest effective absorption bandwidth, reaching 7.0 GHz (11–18 GHz), is attained at a matching thickness of 2.2 mm. The exceptional broadband and reflection loss performance are attributed to the 3D porous networks, interface effects, carbon network defects, and dipole relaxation. HPC has outstanding absorption characteristics due to its excellent impedance matching and high attenuation constant. The uniform pore structures considerably optimize the impedance-matching performance of the material, while the abundance of interfaces and defects enhances the dielectric loss, thereby improving the attenuation constant. Furthermore, the impact of carbonization temperature and swelling rate on microwave absorption performance was systematically investigated. This research presents a strategy for preparing absorbing materials using biomass-derived HPC, showcasing considerable potential in the field of electromagnetic wave absorption.