<p>A new process for vanadium extraction via direct oxidative sodiation and water leaching is proposed, utilizing high-temperature residual heat from molten vanadium slag during vanadium extraction from vanadium–titanium magnetite. This study investigated the effects of cooling methods, Na₂CO₃ dosage, and reaction time on the phase composition of vanadium slag. Under oxygen-rich conditions, molten vanadium slag reacted with Na₂CO₃, converting vanadium into sodium vanadate. The thermodynamic feasibility of key sodiation reactions was evaluated using FactSage 8.1. The results showed that adding 24% (mass fraction) of Na₂CO₃ to molten vanadium slag can produce multiple sodium vanadate phases, significantly improving the leaching rate of vanadium. Additionally, vanadium leaching rate exceeding 90% were achieved under the following conditions: particle size less than 75&#xa0;μm, leaching temperature of 90&#xa0;°C, liquid-to-solid ratio of 10:1, and stirring speed of 300&#xa0;rpm. Compared to conventional methods, this approach reduces processing time, conserves energy, and lowers emissions. Energy-saving calculations indicate that treating 1000&#xa0;kg of vanadium slag with this process would save 1.68 × 10⁶ kJ, equivalent to 57.34&#xa0;kg of standard coal.</p> Graphical Abstract <p></p>