The DA cycloaddition reaction represents one of the most important organic chemical reactions since its discovery in 1928 and it is widely used in the total synthesis of complex products. While a past study indicated that the DA reaction is less favoured over other side-reaction(s) in water microdroplets, exceptions are noted in the literature with the use of strained multi-cyclic hydrocarbon or 'quasi-benzyne' intermediate. This highlights the need to broaden the scope of DA reactions in microdroplets by investigating the factors that either facilitate, inhibit, or have no effect on their occurrence. In addition, the Coote group reported electrostatic catalysis of DA reaction using scanning tunnelling microscopy (STM), providing experimental evidence that the reaction is accelerated by an external electric field. The sprayed microdroplets are rapidly evaporating and/or undergoing fission events. In these cases, the droplet interface is highly chaotic, so the electric field on the microdroplets may dynamically fluctuate, a situation that is quite different to that of the oriented static electric field generated by STM apparatus. This aspect further drives us to explore whether the spontaneous electric field present in microdroplets can affect the kinetics of DA reactions.