It has been recently discovered that chemical reactions at aqueous interfaces can be orders of magnitude faster compared to conventional bulk phase reactions, but despite its wide-ranging implications, which extend from atmospheric to synthetic chemistry or technological applications, the phenomenon is still incompletely understood. The role of strong electric fields due to space asymmetry and the accumulation of ions at the interface has been claimed as a possible cause from some experiments, but the reorganization of the solvent around the reactive system should provide even greater additional electrostatic contributions that have not yet been analyzed. In this study, with the help of first-principles molecular dynamics simulations, we go deeper into this issue by a careful assessment of solvation electrostatics at the air-water interface. Our simulations confirm that electrostatic forces can indeed be a key factor in rate acceleration compared to bulk solution. Remarkably, the study reveals that the effect cannot simply be attributed to the magnitude of the local electric field and that the fluctuations of the full electrostatic potential resulting from unique dynamical behavior of the solvation shells at the interface must be accounted for. This finding paves the way for future applications of the phenomenon in organic synthesis, especially for charge transfer or redox reactions in thin films and microdroplets.