To realize the efficient and clean comprehensive utilization of vanadium–titanium magnetite in the Baima mining area of Panzhihua, an innovative hydrogen‐based shaft furnace direct reduction followed by a melting separation process is proposed. In this study, the melting separation behaviors of vanadium–titanium magnetite affected by the temperature, time, basicity, and C/O (mole ratio of carbon to reducible oxygen) are systematically investigated. The chemical composition, phase composition, and microstructure of slag using modern analytical techniques such as X‐ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy are also revealed. The results revealed that under the optimization conditions including the melting temperature of 1600 °C for 30 min, basicity of 0.50, and C/O of 1.10, the corresponding separation rates of Fe and V in pig iron are 99.31% and 89.73%, and the separation rate of TiO2 in slag is 92.83%, Meanwhile, a preferable characteristic of slag with viscosity of 0.116 Pa s and melting temperature of 1374.54 °C was obtained. The directed migration of valuable elements in vanadium–titanium magnetite is successfully realized.