Vanadium-bearing mica in stone coal vanadium ore serves as one of the important vanadium source minerals. While the presence of oxidizing agents and fluorides significantly enhances vanadium leaching efficiency, the underlying mechanisms remain incompletely understood. This study focuses on the ShanYang stone coal vanadium deposit in Shangluo, Shaanxi Province. Using a thermostatic waterbath-sulfuric acid leaching technique，the effects of oxidizing agents and fluoride systems, including binary fluorides of GroupⅠ, Ⅱ, Ⅲ metals, hydrofluorides (K⁺/Na⁺/${\text{NH}}_4^{+}$), and hexafluoro-silicates/aluminates/phosphates, on vanadium leaching are systematically investigated. Through SEM and element mapping analysis, the primary pathways by which oxidants and fluorides promote vanadium leaching are clarified for the first time. Results indicate that the “pore corrosion” and “crevice corrosion” induced by the oxidant and fluorides are the main ways for efficient vanadium leaching. The effects of Group Ⅰ, Ⅱ metallic fluorides have been found to follow the order: CsF>KF>NaF>LiF, BaF₂>SrF₂>CaF₂>MgF₂，aligning with the lattice energies of these fluorides and the standard Gibbs free energy changes for HF production via reactions of these fluorides with leaching agent(sulfuric acid). In hexafluorosilicate/aluminate/phosphate systems, Na₂SiF₆ predominantly induces “pore corrosion”, while (NH₄)₂SiF₆ generates extensive “crevice corrosion”traces. Faster HF mass transfer in fissure corrosion explains their divergent leaching efficiencies at varying dosages. Na₃AlF₆ forms colloidal aggregates that hinder mass transfer, resulting in lower leaching efficiency compared to (NH4)₃AlF₆, as confirmed by Al mapping in the residues. ${\text{PF}}_6^{-}$ exhibits weaker dissociation than ${\text{SiF}}_6^{2-}$/${\text{AlF}}_6^{3-}$ due to stronger P—F bonds (vs. Si—F/Al—F), making NH₄PF₆ less effective. Hydrofluorides (KHF₂>NH₄HF₂>NaHF₂) achieve superior leaching via “pore corrosion”, with KHF₂ achieving 96.0% vanadium recovery-the highest among all fluorides. SEM confirms the presence of abundant corrosion pores in KHF₂ residues. This work provides theoretical and technical foundations for optimizing vanadium extraction from stone coal.