In this paper we study the selective adsorption of a high molar mass polymer, OSA-starch, at the cyclohexane/water interface during emulsification. This was made possible through the use of AsFlFFF-MALS-RI which enables us to characterize the size and molar mass of polydisperse ultrahigh molar mass polymers. The results show that the high molar mass components in the molar mass distribution of the polymer were selectively adsorbed. The selective adsorption is most likely due to convective mass transport in the turbulent flow fields, during formation of the emulsion, which favors transport to the interface of the high molar mass polymers in the sample. The rapid adsorption that occurs during emulsification is likely to give rise to nonequilibrium effects and jamming at the interface. Furthermore, we describe the adsorption process and illustrate its selective nature through a turbulent flow collision model.