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Long-term high temperature in conventional vanadium extraction process would cause particles to be sintered and wrapped, thus reducing extraction efficiency of vanadium. Based on the purpose of directional conversion and process intensification, this work proposed a combination of low temperature sodium roasting and high ef-ficiency selective oxidation leaching in vanadium extraction. The investigation of the reaction mechanism sug-gested that the structure of vanadium slag was changed by roasting, which also caused the fracture of spinel. The addition of MnO2 promoted the directional oxidation of low-valent vanadium into high valence. It also found that Na2S2O8 could oxidize low-valent vanadium effectively in leaching. The leaching efficiency of vana-dium reached 87.74%under the optimum conditions, including a roasting temperature of 650 ℃, a roasting time of 2.0 h, a molar ratio of sodium-to-vanadium of 0.6, a MnO2 (roasting additive) dosage of 5 wt%and a Na2S2O8 (leaching oxidant) dosage of 5 wt%. This percentage is 7.18%higher than that of direct roasting-and-leaching under the same conditions.