Binary systems with partial miscibility segregate into two liquid phases when their overall composition lies within the interval defined by the saturation points; out of this interval, there is one single phase, either solvent-rich or solute-rich. In most systems, in the one-phase regions, surface tension decreases with increasing solute concentration due to solute adsorption at the liquid air interface. Therefore, the solute concentration at the surface is higher than in the bulk, leading to the hypothesis that phase segregation starts at the liquid air interface with the formation of two surface phases, before the liquid liquid equilibrium. This phenomenon is called surface segregation and is a step toward understanding liquid segregation at a molecular level and detailing the constitution of fluid interfaces. Surface segregation of aqueous binary systems of alkyl acetates with partial miscibility was theoretically demonstrated by means of a thermodynamic stability test based on energy minimization. Experimentally, the coexistence of two surface regions was verified through Brewster's angle microscopy. The observations were further interpreted with the aid of molecular dynamics simulations, which show the diffusion of the acetates from the bulk toward the liquid air interface, where acetates aggregate into acetate-rich domains.