AbstractVentilation air methane (VAM) is one of the main greenhouse gas sources. Owing to the characteristics of low concentration of ventilation air methane and high moisture content, we build an experimental platform and take the oxidative combustion temperature and methane conversion rate as the research indexes, and the systematic research finds that the inhibitory effect of moisture on the oxidative combustion of ultra‐low concentration of methane (<1%) is a nonlinear polynomial law. In the meantime, we constructed OH(H2O)n+CH4 and studied its reaction potential energy surface using quantum chemical calculations, which used the most significant primitive reaction of methane combustion, OH+CH4→H2O+CH3, as the theoretical basis. We found that as moisture content increased, so did its reaction energy barrier, making the reactants more stable, strengthening the three‐body collision effect, and reducing the number of free radicals, all of which hindered the methane chain reaction. The study aimed to validate the experimental finding that moisture inhibits the oxidative combustion of ventilation air methane by examining the internal mechanism of methane oxidation. © 2024 Society of Chemical Industry and John Wiley & Sons, Ltd.