<p>In order to investigate the extraction and utilization of vanadium resources in titanium tetrachloride refining tailings, on the basis of traditional sodium calcination, the NaCl–Na₂CO₃ composite calcination-water leaching process for vanadium extraction was proposed. The study focused on the influence of calcination and leaching process conditions on the physical composition and vanadium leaching rate of calcined clinker, and ultimately to determine the optimal process conditions, and to explore the leaching kinetics. The synergistic effect of NaCl–Na₂CO₃ accelerated the oxidation of vanadium-iron spinel, enhancing vanadate generation while reducing consumption of single sodium salt, ultimately significantly improving the vanadium leaching rate. Under the following conditions: m(NaCl):m(Na₂CO₃) = 3:2, calcination temperature of 800&#xa0;°C, calcination time of 3&#xa0;h, leaching temperature of 70&#xa0;°C, leaching time of 90&#xa0;min and liquid–solid ratio of 10:1&#xa0;mL/g, the vanadium leaching rate of NaCl–Na₂CO₃ composite calcination was 93.84%, which was 4.43% higher than that of single NaCl as the calcination additive. The vanadium leaching process was in accordance with the shrinking core model, which is controlled by both chemical reaction and diffusion mechanisms. The apparent activation energy of this process is 39.81&#xa0;kJ/mol.</p> Graphical Abstract <p></p>