Mn-corrolazine-catalyzed CH 4 oxidation, as well as the regulation of its oriented external electric fields (OEEFs), is systematically studied using the first-principle calculations. Extensive density functional calculations show that the activation energy of CH 4 oxidation catalyzed by Mn-corrolazine is up to 38.5 kcal/mol in the field-free condition. However, when the OEEF is applied, the reactant and the transition state of the oxidation reaction are stabilized, originating from an attractive interaction between the increased dipole moment and the applied fields. Furthermore, when the field is negative, the activation energy decreases as the field increases. Especially for the negative field along the intrinsic Mn O reaction axis perpendicular to the corrolazine ring, of which the orientation is easily aligned in practical applications, when its intensity reaches −0.015 a.u., the activation energy of CH 4 oxidation is reduced to 25.0 kcal/mol. K E Y W O R D S catalysis, CH 4 oxidation, density functional theory calculations, Mn-corrolazine, oriented external electric field 1 | INTRODUCTION Searching for novel and efficient catalysts has always been the most important subject in chemical research. Traditionally, the common catalysts are molecules and the surfaces or interface in homogeneous and heterogeneous systems, [1-6] respectively. However, in recent years, many new technologies, such as ultrasound, [7] microwaves, [8] mechanical stress, [9] and nanoreactors, [10] have been used to control various reaction processes as novel catalysts. Electrostatic forces play an extremely important role in chemical reactions involving the arrangement of nuclei and electrons. [11-13] A typical example is the electrostatic catalysis of enzymes in nature. [10,14-16] The polar environment originating from the subtle arrangement of atoms around the active site produces the electric field that can efficiently and selectively catalyze various biochemical reactions. Using the same idea, research is increasingly focused on regulating the stability of the reactants and transition states, as well as products, using artificial external electric fields through dipole-field interaction, thereby manipulating the chemical reaction process. [17-44] Very recently, Shaik et al. performed a much computational research to explore the effect of oriented external electric fields (OEEFs) on organic reactions. [17-23] Their research results show that OFFEs along the reaction axis involving the electron transfer can significantly catalyze the organic reactions, while the OFFEs along other directions can control the regioselectivity and stereoselectivity, and some results are confirmed by experimental evidence provided by Aragonès et al. [18] However, although great progress has been made in both the experimental and theoretical research, [17-24,27,30] a major problem in using the OFFEs to manipulate reaction processes is to deliver the external electric fields and orient the molecules within the applied fields simultaneously. The corrole, a porph...