We measured the fractional abundance of DA products across all products (Ox1, Ox2, DA1, and DA2) in the mass spectra recorded by tuning the spray parameters. Microdroplets formed using a 0V spray (see Figure ) typically carry net charges, mostly attributed to the statistical fluctuations of ions like H + and OH¯ during the gas-assisted atomization of water. Earlier reports demonstrated that when a spray potential is applied, there is a dramatic increase in droplet charging (>100-fold), likely facilitated by the solvent redox process (electrospray charging). Therefore, when we gradually increased the spray potential to +5 kV, producing highly charged microdroplets, this likely intensified the IEF due to an increased net surface charge. Subsequently, we observed a significant reduction in the extent of the DA reaction in water droplets as compared to those in acetonitrile droplets (Figure ). This result indicates a marked preference for oxidation reactions at the charged surface of water microdroplets at the expense of the competing DA reactions (Figure ), which may not prefer the charged environment of the droplet and, hence, the associated EF at the surface. In other words, the IEF has a negligible role in promoting the DA reactions, as predicted by our simulations using both water and acetonitrile as solvent (Table ). Instead, the IEF triggers oxidation reactions.