Polymetallic vanadium titano-magnetite (VTM) is recognized as one of the most refractory mineral resources because of its multiple-element composite symbiosis feature. Conventional carbothermic reduction and smelting separation treatment are characterized by high energy consumption and large greenhouse gas emissions. Considering the material attribute, an alternative and clean utilization of refractory VTM via the pyrometallurgically oriented phase transformation in air atmosphere to prepare the composite electromagnetic wave absorbing material was proposed for the first time in this work. The theoretical foundation of the oriented composite material design, phase transformation, microstructure and interfacial element migration, magnetism, electromagnetic properties, and wave absorbing properties were investigated via thermodynamic calculations, XRD, XPS, optical microscope, SEM‒EDS, VSM, and VNA analyses. Theoretical calculations indicated that the formation of composite ferrites was thermodynamically feasible over 1085 °C. In the oriented phase reconstruction, the symbiotic structure of the VTM was reconstructed via MnO2 addition at 1150 °C, and almost all the Fe, Mn, Ti, and V were concentrated in the composite ferrites, in which the Ti and V were doped in the octahedral structure (B site) of spinel-type crystalline structure. The as-purified composite ferrite material from the VTM+80%MnO2 mixture roasted at 1150 °C for 2 h showed good electromagnetism performance. A minimum RL peak of −50 dB was obtained at a veneer thickness of 11 mm, and the RL value less than −20 dB had a big frequency bandwidth of 9 GHz (frequency range of 8 GHz–17 GHz). It's inferred that this low-cost and abundant composite ferrite material can be economically applied in the construction industry. This work provided a clean and higher-value application of abundant refractory polymetallic VTM resources.