Oil-in-water (O/W) emulsions were prepared using exclusively a hydrophobically modified xanthan (HMX) under ordered conformation without any surfactant. A series of HMX differing in grafting density were utilized at different concentrations. It was demonstrated that HMX stabilizes O/W emulsions where pristine xanthan do not. Indeed, in some cases, emulsions with HMX proved to be homogeneous and stable over months. Emulsions microstructure and rheological properties were investigated over time as a function of HMX concentration and grafting density in order to determine the mechanisms governing this efficient stability. The higher the HMX concentration is, the better the emulsions stability. However, unexpectedly, increasing the HMX grafting density leads to faster destabilization. The whole set of results demonstrate that the stability of the emulsions against coalescence and creaming is explained by partitioning of HMX molecules between bulk and interface, thus split between viscosifying the aqueous phase and stabilizing the interface.