Although cyclodextrins (CDs) have been used as additives to small molecule surfactants, there are only a few examples of this cyclic oligosaccharide being used as a surfactant template. Herein, we present a novel ionic β-CD derivative that shows significant surface activity and stabilizes oil-in-water emulsions prepared with hexadecane as a model oil. The macrocyclic surfactant strongly reduces the oil-water surface tension with increasing concentration and shows a critical micelle concentration (CMC) around 5 mM. We demonstrate the stability of the oil-in-water emulsions and verify the possibility to address the emulsion droplet surface using molecular recognition of the β-CD cavity at the oil-water interface.