This study innovated the concept in designing an efficient and reusable microwave (MW) absorbent through concurrent exploitation of carbon graphitization, oxygen functionalization, and carbothermal iron reduction underpinned by an endothermic co-pyrolysis of wood waste and low-dosage iron. A powerful MW assimilation was accomplished from nanoscale amorphous magnetic particles as well as graphitized microporous carbon-iron skeleton in the biochar composites. Relative to a weak magnetic loss derived from the iron phase, the graphitic carbon architecture with abundant surface functionalities (i.e., CO and CO) exhibited a strong dielectric loss, which was thus prioritized as major active sites during MW reuse. The MW-absorbing biochar demonstrated a fast, robust, and durable removal of a refractory herbicide (2,4-dichlorophenoxy acetic acid) under mild MW irradiation with zero chemical input, low electricity consumption, and negligible Fe dissolution. Overall, this study will foster carbon-neutral industrial wastewater treatment and wood waste valorization.