The stability of oil-in-water emulsions prepared using dextran, a natural polysaccharide, hydrophobically substituted with phenoxy groups, was studied. The evolution of the emulsion droplet size was investigated as a function of polymer concentration (Cp = 0.2 to 1% w/w in a water phase) and the degree of phenoxy substitution (tau = 4.2 to 15.7%). For the highest tau values, emulsions, which presented submicrometer droplets, were stable over more than 4 months at room temperature. The most substituted polymers clearly showed a better efficiency to lower the surface tension at the oil/water interface. DexP did not induce real viscosification of the continuous phase. The linearity of the particle volume variation with time, and the invariability of the volume distribution function, proved that Ostwald ripening was the main destabilization mechanism of the phenoxy dextran emulsions. The nature of the oil dispersed phase drastically affected the behavior of emulsions. While the emulsions prepared with n-dodecane presented a particle growth with time, only few size variations occurred when n-hexadecane was used. Furthermore, small ratios of n-hexadecane in n-dodecane phase reduced the particle growth due to the lower solubility and lower diffusion coefficient in water of n-hexadecane, which acted as a ripening inhibitor.