As typical dielectric materials, transition metal compounds have a broad potential in the field of stealth, but their application is still hampered by poor conductivity. In this study, based on the mechanism of electrostatic self-assembly of heteropolyacids and organic ligands, the electrostatic structures obtained after the introduction of different heteropolyacids into the conductive phase pyrrole are carbonized. On the one hand, the as-prepared transition metal compounds/carbon matrix nanocomposites produce synergistic effects and optimize impedance matching, and on the other hand, the formation of the abundant heterogeneous interfaces as well as the doping of the N, P heteroatoms induce the generation of interfacial polarization and dipole polarization, all of which provide the opportunities to produce composites with enhanced electromagnetic wave absorption properties. Unsurprisingly, the best synthesised sample, Mo2C/W2C/NPC, exhibits a significantly improved electromagnetic wave absorption performance, with an effective bandwidth of 5.7 GHz at a matched thickness of 2.5 mm, where the minimum reflection loss value of -54.5 dB is also achieved. The total effective bandwidth of the Mo2C/W2C/NPC-35wt% is up to 10.5 GHz (7.3-17.8 GHz) via adjusting the matching thickness in the range of 1.7-3.5 mm. Therefore, this study reflects that dual transition metal compound/carbon based composite wave-absorbing materials provide a new material basis for the construction of high-performance absorption materials.