A series of innovative green metallurgical processes using novel reaction media including the NaOH/KOH sub-molten salt media and the NaOH-NaNO3 binary molten salt medium, for the extraction of vanadium and chromium from the vanadium slag have been developed. In comparison with the traditional sodium salt roasting technology, which operates at 850 ℃, the operation temperatures of these new processes drop to 200-400 ℃. Further, the extraction rates of vanadium and chromium utilizing the new approaches could reach 95% and 90%, respectively, significantly higher than those in the traditional roasting process, which are 75% and approximate zero, respectively. Besides, no hazardous gases and toxic tailings are discharged during the extraction process. Compared with the conventional roasting method, these new technologies show obvious advantages in terms of energy, environments, and the mineral resource utilization efficiency, providing an attractive alternative for the green technology upgrade of the vanadium production industries.