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SF₆ will decompose to several byproducts (including SOF₂, SO₂F₂, SO₂, etc.) under corona discharge. Macro features of SF₆ decomposition are closely linked with the micro decomposition process. A quantum chemistry analysis combining density functional theory (DFT) was used in this paper to study the complex decomposition process of SF₆ in detail. A decomposition model of SF₆ with two typical zones was then established. Electron distribution of low fluoride sulfides shows that (SF₂)^* and (SF₄)^* are relatively stable. Formation pathways, reaction rate constants, and reaction region of SOF₄, SOF₂, SO₂F₂, SO₂ were derived. SOF₄ mainly comes from dissociation of SF₅OH generating by oxidation between (SF₅)^* and OH^*. SO₂F₂ is mainly generated through the oxidation reaction between (SF₂)^* and O^* in the high-energy region. SOF₂ and SO₂ are both generated through hydrolysis reaction in the low …