In non‐metallic atom‐doped carbonaceous materials, the disparity in electronegativity between the doped constituents and carbon atoms predetermines the bonding topology of covalent bonds and the distribution of electron density. This, consequently, influences the polarization and electron transport behavior within the doped domain and the electromagnetic wave attenuation attributes of the carbonaceous material. However, the influence of covalent bonds formed by doping with weakly electronegative atoms on electron density distribution, polarization effects, and electromagnetic wave attenuation remains uncharted. To address this deficiency, this study fabricates a porous carbonaceous material (NCP) and incorporates boron‐doped atoms to form a material with tunable B─C bonding configurations (B‐NCP). By modulating the B─C bonding configuration and proportion, it is feasible to achieve the synergistic optimization of conductive loss and polarization loss of the B‐NCP specimen. The optimized prototype B‐NCP‐1200 sample displays exceptionally efficient electromagnetic wave absorption capabilities with a minimum reflection loss (RLmin) of −52.03 dB and an effective absorption bandwidth (EAB) of 5.36 GHz. This study presents a conscientious model for comprehending the electromagnetic attenuation mechanisms associated with weakly electronegative atom doping in carbon‐based electromagnetic wave‐absorbing materials.