Abstract: Copper⁃based zeolite catalyst has the catalytic ability for the direct oxidation of methane to methanol under low⁃temperature conditions. Based on the structure and stability differences of Cu2O22+ -ZSM-5 formed by the pre⁃ treatment of O2 on Cu2 2+ -ZSM-5，the successive processes of Cu2 O2 2+ -ZSM-5→Cu2 O2+ -ZSM-5→ Cu2 2+ -ZSM-5 to catalyze the direct oxidation of methane to methanol were investigated by employing density func⁃ tional theory. The purpose is to obtain the structure of Cu2Ox2+-ZSM-5 (x=1，2) catalysts and the catalytic per⁃ formances for the direct oxidation of methane to methanol. The results show that the Cu2 2+ - ZSM - 5 prefers to form three kinds of Cu2O22+-ZSM-5 configurations involving O—O bond that the (CuO)22+ -ZSM-5，CuOOCu2+ - ZSM-5 and CuO2Cu2+ -ZSM-5 while the break of O—O bond leads to CuOCuO2+ -ZSM-5 configuration with poor stability requiring high temperature and formation energy barrier. All of (CuO)22+ -ZSM-5，CuOOCu2+ -ZSM-5 and CuO2Cu2+ -ZSM-5 as well as Cu2O2+ -ZSM-5 can catalyze the direct oxidation of methane to meth⁃ anol. The CuO2Cu2+ -ZSM-5 presents the highest catalytic performances where the determining⁃step is the dissocia⁃ tion of adsorbed CH4 with the energy barrier of the determining⁃step of 150.69 kJl/mol and the total reaction energy of -131.60 kJ/mol. The analysis of electronic structure indicates the correlation of high catalytic performance with a high level of electron delocalization and close p⁃band center relative to the Fermi level.