[en] The mechanism of ethylene oxidation to ethylene glycol on the permanganate material has been investigated by density functional theory with the M06-L functionals. Effect of the BF₃ coordination to the MnO₄⁻ on the mechanism has been examined in details. The initial step is the activation of ethylene C=C bond via the [3+2] electrocyclic addition. The calculated reaction barrier of this step on MnO₄⁻ material (53.67 kJ mol⁻¹) is decreased significantly with the presence of BF₃ (32.37 kJ mol⁻¹). In the next step of cyclic intermediate hydration to ethylene glycol, the activation energies for the first and second hydrations are 136.14 and 93.03 kJ mol⁻¹ on BF₃–MnO₄⁻, and 147.08 and 134.87 kJ mol⁻¹ on MnO₄⁻. These results demonstrate that the BF₃ coordinated to the MnO₄⁻ material can enhance the overall conversion of ethylene to ethylene glycol. Molecular orbital analysis provides more understanding regarding the role of BF₃ in this reaction. Graphical abstract: < Image>.