The emulsification properties of hydrophobically modified xanthan (HMX) obtained through green esterification using alkenyl succinic anhydrides (ASA) as grafting agents were investigated by preparing oil-in-water emulsions without adding any surfactant, in order to better understand the stability phenomenon at the oil-water interface. This study demonstrated that new-brand bio-sourced HMX owns emulsifying potential compared to pristine xanthane, known for its poor interfacial properties as a non-absorbing polymer. A complete approach for studying the stability of the dispersions was carried out at different levels: a) macroscopic level: visual identification of stability, b) microscopic level: coupled optical microscopy and droplet size distribution and c) deep microstructure stability monitoring over time by Static Multiple Light Scattering. First, a series of HMX differing in alkenyl chain length and grafting density added at 0.2% w/w in emulsions were compared. Increased grafting density or hydrophobic chain length provided a highly stable and homogeneous emulsion over 30 days. In the case of less stable emulsions, two solutions are proposed: 1) increasing HMX concentration thus improving emulsifying properties, 2) adding native xanthan as a thickening agent, which slows down the creaming destabilization mechanism. This original article shows that the new-brand bio-sourced amphiphilic xanthan obtained under green modification synthesis behave promising and effective emulsifying capacities to stabilize oil-in-water emulsions, which offers promising potential for industrial applications.