Methane combustion plays an important role in various fields such as combustion chemistry and atmospheric chemistry of the stratosphere. Highly accurate study of its initial reaction remains a key challenge. Here, through extensive studies with a state-of-the-art ab initio and neural network method, we present a potential energy surface of the O(3P) + CH4 → OH + CH3 reaction on the ground state 13A and the first excited state 23A. In this work, the energies of 10 167 points covering all important regions are obtained with state-averaged complete active space self-consistent field calculations and then fitted using the Levenberg-Marquardt algorithm with a root-mean-square error of 0.391 and 0.442 kcal/mol for the 13A and 23A states, respectively. This study explores the characteristics of the radical van der Waals (VdW) complex and reveals a detailed mechanism of the methane combustion initial reaction. Within the scope of this mechanism, this surface gives a fairly accurate description of the regions around the saddle point, conical intersection, and vdW wells in the entrance for efficient computational simulations. As a theoretical study on a prototypical polyatomic reaction, it is hopeful that this work will modify our understanding of the primary process in hydrocarbon combustion.