This contribution focuses on the spatial‐temporal behavior and reactive pathways of O3 produced by a surface air microdischarge in the gas and liquid phase using ultraviolet absorption spectroscopy. The findings demonstrate that mode transition from ozone to nitrogen oxide over time is observed at a constant input power higher than ~0.60 W/cm2. Due to the long‐lived characteristic and ionic wind, the perpendicular distribution of O3 is almost uniform. The maximum penetration depth is around 5 mm, and the gas–liquid mass transfer efficiency is approximately 0.4‱ at a depth of 1 mm, when the treatment time is 10 min. The mass transfer of O3 between gas and liquid phases is dominated by the liquid convention induced by ionic wind.