The mechanisms of aid-leaching reagent calcium fluoride in the extracting vanadium processes were researched by comparing the blank extraction with the extraction with calcium fluoride as aid-leaching reagent. The leaching experiments were carried out under the conditions of 95 ℃, 6h, 1.5 mlg-1 , 15 vol % H2SO4 , and 5 % calcium fluoride (mass ratio of CaF2 to stone coal). The concentrations of hydrogen ion were adjusted from initial 1.82 and 4.79 mol L -1 to the pH of 1.80 ± 0.05 by 200 g L-1 lime milk, respectively. The solvent extraction experiments were carried out under the organic phase using 15 vol% D2EHPA, 5 vol% TBP, and 80 vol% sulfonated kerosene and O/A phase ratio of 1/4. The leaching rate of vanadium and six-stage countercurrent solvent extraction rate of vanadium can be remarkably improved from 66.71 to 92.97 % and 81.15 to 98.81 %, respectively, when calcium fluoride was added as aid-leaching reagent. In the leaching process, fluorine can enhance the breakage of the structure of vanadium-bearing minerals. Meanwhile, fluoride ion can combine with iron ion to generate acid-insoluble iron fluoride hydrate (Fe2F57H2O) and consume all ferric ions and a portion of ferrous ions. In adjusting pH value process, the massive impurities are decreased to form KAlSO4 and FeAlF5 . In solvent extraction process, fluorine can prevent the formation of ferric hydroxide colloids and eliminate the formed unstable ferric hydroxide colloids and the silicon-containing colloids to promote the sufficient contact between the aqueous phase and the organic phase and the sufficient reaction. The mechanisms of aid-leaching reagent calcium fluoride in extracting vanadium processes were researched by comparing the blank extraction with the extraction with calcium fluoride as aid-leaching reagent. The leaching experiments were carried out under the conditions of 95 ° C., 6 h, 1.5 mlg -1, 15 vol% H2SO4, and 5% calcium fluoride (mass ratio of CaF2 to stone coal). The concentrations of hydrogen ion were adjusted from initial 1.82 and 4.79 mol L "1 to the pH of 1.80 ± 0.05 by 200 g L -1 lime milk, respectively. The solvent extraction experiments were carried out under the organic phase using 15 vol% D2EHPA, 5 vol% TBP, and 80 vol% sulfonated kerosene and O / A phase ratio of 1/4. vanadium and six-stage countercurrent solvent extraction rate of vanadium can remarkably improved from 66.71 to 92.97% and 81.15 to 98.81%, respectively, when calcium fluoride was added as aid-leaching reagent. In the leaching process, fluorine can enhance the breakage of the Structure of vanadium-bearing minerals. Meanwhile, fluoride ion can combine with iron ion to generate acid-insoluble iron fluoride hydrate (Fe2F57H2O) and consume all ferric ions and a portion of ferrous ions. to form KAlSO4 and FeAlF5. In solvent extraction process, fluorine can prevent the formation of ferric hydroxide colloids and eliminate the formed unstable ferric hydroxide colloids and the silicon-containing colloids to promote the sufficient contact between the aqueous phase and the organic phase and the sufficient reaction.