Surfactants have been used for decades in the food industry for the preparation of lipid-based emulsified food stuffs. They play two main roles in the emulsification processes: first they decrease the interfacial tension between the oil and water, facilitating droplet deformation and rupture; second, they reduce droplet coalescence by forming steric barriers. However, addition of surfactants to binary oil-water mixtures also brings up the formation of three-dimensional interfacial layers, surrounding each emulsion droplet, that significantly alter chemical reactivity. This is the case, for instance, in the inhibition reaction between antioxidants and the lipid radicals formed in the course of the spontaneous oxidation reaction of unsaturated lipids, which are commonly employed in the preparation of food-grade emulsions. The rate of the inhibition reaction depends on the effective concentrations of antioxidants, which are mostly controlled by the amount of surfactant employed in the preparation of the emulsion. In this work, we analyze the effects of the surfactant Tween 20 on the oxidative stability and on the effective concentrations of two model antioxidants derived from cinnamic acid, determining their interfacial concentrations in the intact emulsions to avoid disrupting the existing equilibria and biasing results. For this purpose, a recently developed methodology was employed, and experimental results were interpreted on the grounds of a pseudophase kinetic model.