The properties and applications of nanoemulsions are critically governed by the interfacial composition at the oil-water interface.Conventional techniques, which primarily simulate interfacial behavior, exhibit notable limitations in capturing authentic mol. arrangements.In contrast, the chem. trapping (CT) method enables in situ probing of interfacial composition, offering mol.-level insights into nanoemulsion behavior.Here, sodium lauryl Me taurine (SLMT) and cetyltrimethylammonium bromide (CTAB) nanoemulsions were prepared under different surfactant concentrations, oil fractions, homogenization methods (high-pressure homogenization vs. ultrasonication), and salt addition conditions.The emulsions were characterized by dynamic light scattering (DLS) and stability anal., while their interfacial compositions were investigated using the CT method, providing mol.-level insights into droplet size and stability changes.The results revealed that changes in surfactant concentration and oil fraction directly impacted droplet size and emulsion stability, corresponding to shifts in interfacial molarities.Addnl., nanoemulsions produced via ultrasonication displayed interfacial properties comparable to those produced by high-pressure homogenization, validating ultrasonication as a scalable alternative.Notably, SLMT emulsions displayed ion-specific effects: tetrapropylammonium (TPA+) and tetraethylammonium (TEA+) ions formed ion pairs with sulfonate headgroups, displacing interfacial water, enhancing mol. packing, and reducing curvature, thereby increasing droplet size.These results establish a direct structure-property relationship between interfacial composition and nanoemulsion performance, providing a rational framework for designing functional nanoemulsions in food, cosmetics, and pharmaceutical applications.