<p>Microwave pre-oxidation and biomass reduction were adopted to enhance the separation of titanium and iron in vanadium–titanium magnetite. The effects of microwave pre-oxidation temperature and time, as well as biomass reduction temperature and time, were investigated. The results showed that the average particle size of vanadium–titanium magnetite decreased, and the specific surface area increased with the increase in pre-oxidation temperature and time. The reaction pathway (Fe_3−<i>x</i>Ti_<i>x</i>O₄ → Fe_2−<i>x</i>Ti_<i>x</i>O₃ → Fe₂TiO₅) was proved in microwave pre-oxidation process. The results of biomass reduction roasting showed that biomass reduction could effectively reduce ferric oxide to metallic iron while Ti was enriched in a solid solution of magnesium anosovite, which was beneficial to the subsequent grinding and acid leaching separation. The combined process of microwave pre-oxidation and biomass reduction achieved a high separation efficiency of titanium and iron in vanadium–titanium magnetite without forming complex titanium minerals. The titanium grade in the vanadium–titanium-rich material was 32.10%, and the recovery rate was 91.51%. The iron grade in the iron concentrate (metallic iron) was 90.90%, the recovery rate was 93.47%, and metallization rate was 93.87%.</p>