With the aim of separating Fe and V, a vanadium-titanium magnetite concentrate was selectively reduced, followed by magnetic separation. The processes accompanying reduction of the vanadium-titanium magnetite concentrate were investigated using thermodynamic simulation, experiments, scanning electron microscopy, and electron probe microanalysis. Appropriate reduction conditions and controlling the amount of CaCO3 promoted the reduction of Fe-containing minerals to metallic Fe. V was released from magnetite, ilmenite, and titanomagnetite, and was inhibited to reduce to metallic V, leading to V enrichment in the non-magnetic products in the form of oxides. Moreover, the Fe particles wrapped the slag phase when the amount of CaCO3 exceeded 8%, which is unfavourable for the magnetic separation of Fe and V. Magnetic products with an Fe content of 87.19%, Fe recovery of 82.62%, V content of 0.09% and non-magnetic products with a V content of 1.00% and a V recovery of 85.49% were obtained when the vanadium-titanium magnetite concentrate was reduced for 100 min at 1623 K with a C/O molar ratio of 2.5 and 8% CaCO3, followed by separating at a magnetic field strength of 85 mT.