Experimentally, the DA reaction is not as highly favored as oxidation reactions in water microdroplets. However, the detection of trace levels (0.02%) of DA products from the reaction between dicyclopentadiene and acrylonitrile in water microdroplets is attributed to the surface enrichment of these hydrophobic reactants on the droplet surface. The increased polarity (or charge) or electric field on such droplet surfaces inhibits the DA reaction by promoting substrate oxidation, indicating that the local electric field does not facilitate the DA reaction at the air-water interface. Additionally, the study, dependent on spray parameters, revealed that while the DA reaction might occur at the surface of water microdroplets, it prefers to occur within the core of acetonitrile droplets, suggesting that partial solvation is not necessarily a critical factor for this reaction. Instead, the rapid evaporation of microdroplets and the subsequent reagent enrichment within the accessible confined volume of microdroplets are the driving force for acceleration of the DA reaction in microdroplets. We also emphasize that the conclusions drawn above are based on a single DA reaction and may not necessarily apply universally to other reactions, as the specific factors accelerating each reaction type can vary. Overall, the reactivity enhancement in microdroplet is a result of multiple factors working in concert, and our combined computational and experimental efforts are dedicated to dissecting the contribution of each factor to such a model reaction. However, further research is expected to provide better insights into these aspects in the next future. This work provides insights for manipulating reactions in water microdroplets, offering potential perspectives on leveraging water microdroplet chemistry for future applications.