In oxidation reactions with oxygen as oxidant, low O2 concentration on catalyst surface under ambient pressure is a major kinetic limitation for selective oxidation of olefins; while increasing O2 pressure to enhance the reaction rate suffers lower selectivity due to thermodynamic factors. In this study, we demonstrate that simultaneous enhancement of conversion and selectivity can be achieved under ambient pressure by solid/liquid/gas three-phase interface design. We produced Au nanoparticles supported on graphene aerogel with superaerophilic surface (denoted as Au/GA) as the catalyst for demonstration. The results show that O2 gas shows “bursting” behavior on the surface of Au/GA under water, resulting in rapid adsorbing of O2 in 98 ms and therefore high O2 concentration on the surface of catalyst. Thus, solid/liquid/gas three-phase interface is formed under this condition, leading to high conversion as well as high selectivity at ambient O2 pressure. Such strategy is expected to find wide applications in many other selective oxidation reactions that traditionally needed high pressure.