In view of the unclear cause of perfluorocarbons (PFCs) emission in the anode effect stage of aluminum electrolysis, the microscopic formation mechanism of PFCs was studied by density functional theory calculation and X-ray photoelectron spectroscopy (XPS). It is found that the discharge of fluorine containing anions ([F]^-) on carbon anode first causes the substitution of C—H by C—F and further results in the saturation of aromatic C—C bonds, leading to the appearance of —CF₃ or —C₂F₅ group through six-carbon-ring opening. Elimination of —CF₃ and —C₂F₅ with F atom could be a likely mechanism of CF₄ and C₂F₆ formation. XPS results confirm that different types of —CF_x group can be formed on anode surface during electrolysis, and the possibility that [F]^- discharges continuously at the C edge and finally forms different C—F bonds in quantum mechanical calculation was verified.