Polymeric emulsifiers based on glycerol and oleic acid were developed and their properties evaluated in palm oil and water solutions. Developed polymeric emulsifiers were polyglycerol-esters. Polymerization degree of polyglycerol-esters at different dosages (from 0.2 to 3% w/v) had a significant effect over emulsion stability, water surface tension, droplet size, and viscosity. Polyglycerol-ester with highest polymerization degree behaved more efficiently as emulsifier. A dosage of 0.5% w/v was required to maintain emulsion stability for a half-life period of 872 min (~14.5 h); which, is 5.6 and 3.6-fold longer stability than with the other two polyglycerol-esters developed. When dosage increased to 3% w/v, the emulsion stability also increased to 3792 min (~2.6 days). Nevertheless, surfactants with lower polymerization degree and molecular weight did not behave the same way. Emulsifier with highest polymerization degree reduced water surface tension by 70% and the mean particle diameter decreased when emulsifier polymerization degree increased. For the viscosity parameter, there were two interesting regions: for shear rates up to 1 s −1 the emulsion behaved as Non-Newtonian fluid type Shear-thinning; while, higher shear rates, the viscosity exhibited a Newtonian profile.