Abstract: Microdroplets have many unique features such as small size and high electric field, therefore they can be accelerated to initiate chemical reactions and even promote some reactions that cannot be carried out in liquid phase. N, N-Dimethylaniline (DMA) is commonly used in medicine as a raw material for the synthesis of pharmaceutical intermediates. At present, the study involving in the detection of DMA is mainly focused on quantitative detection, and there is few reports on oxidation reaction and gas phase dissociation reaction of DMA. In this paper, the oxidation behavior and dissociation reaction of DMA and related compounds were studied by microdroplet spray mass spectrometry and tandem mass spectrometry. It was found that the ultra-high electric field spontaneously generated by microdroplets at the air-water interface can enable the oxidation reaction of DMA and related compounds to form abundant radical cation DMA^+·. By changing the reaction distance, carrier gas pressure, injection velocity, sample concentration and substituent groups, the influence of experimental conditions and substituent modes on the generation of DMA^+· was explored. The result showed that the presence of electron donor groups is benefit for the stability of radical cations. After the dissociation of DMA^+·, the main product ions were generated by elimination of hydrogen radical and a successive elimination of HC≡N via methyl migration reaction. In addition, when the electron-donating CH₃ group was connected with DMA, the intensity of related radical cation increased obviously, indicating that the electron-donating groups promoted the migration reaction. In conclusion, the stable transient intermediate DMA^+· that is difficult to prepare by other means, was obtained by microdroplet reaction in this study. This method is helpful to deepen the understanding of the chemical promoted oxidation reaction characteristics of water droplets and enriches the rearrangement reaction types of aniline compounds in gas phase dissociation. It is expected that the prepared active species such as high reactivity radical cations will be applied to chemical industry or pharmaceutical fields in the future.