A family of emulsification curves has been systematically prepared in order to determine the extent of interfacial modifier migration to the high density polyethylene (HDPE)/polystyrene (PS) interface. Through an examination of the evolution of the equilibrium dispersed phase size after interfacial saturation, as well as a comparison of the apparent interfacial area occupied per modifier molecule (Aapp) at the different dispersed phase concentrations, it is possible to detect the onset of micelle formation and to estimate the extent of interfacial coverage. This approach has been applied to HDPE/PS blends, using a variety of triblock and diblock copolymer interfacial modifiers for that system. It is shown quantitatively that it is the affinity of the block copolymer for the matrix material that dominates migration efficacy to the interface. Asymmetrical block copolymers (3OPS/70EB) show a strong tendency to form micelles when HDPE is the matrix. This effect is virtually eliminated when PS is the matrix material or when symmetrical block copolymers (50PS/50EB) are used. In these latter cases all the interfacial modifier finds its way to the interface.