In this work, a novel process of pellet non-salt roasting and H2SO4 leaching was proposed for the selective extraction of vanadium from vanadium–titanium magnetite concentrate. Vanadium can be leached but the iron impurity was maintained in the pellets. Moreover, the leached pellets can meet the quality requirements of the iron-making process after secondary roasting, realizing comprehensive utilization. The maximal vanadium leaching efficiency was up to 60.3%, whereas 0.17% of the iron impurity was leached. The optimum conditions of pellet roasting and leaching were obtained by single-factor experiments. The X-ray diffraction and scanning electron microscopy–energy disperse X-ray spectrometry analyses showed that the vanadium iron spinel can be oxidized and decomposed into Fe2O3 and vanadate during the roasting process. Given that dilute sulfuric acid can react with vanadate without reacting with Fe2O3 in the leaching process, selective vanadium extraction was realized. This work provides new insights into the industrial production of vanadium–titanium magnetite concentrate involving the direct extraction of vanadium.