It is important from both a strategic and economic standpoint to study the mechanism of formation of water/oil emulsions, to predict their increase of viscosity with respect to that of the crude oil, and to obtain information about the stability vs separation of these substances (since their presence can impair oil processing and distribution). The objective of this work was to ascertain the influence of monoethylene glycol (MEG) on these parameters and its action mechanism. The addition of MEG in different proportions in the oil emulsions significantly changed the flow curve of the emulsion, passing from a quasi‐Newtonian one to a shear thinning behaviour. Besides this, when MEG was present at low concentrations, the demulsification process was slow and an increase in concentration made the emulsions more stable than samples containing the same aqueous phase proportion. Under the conditions studied, the addition of MEG did not reduce the quantity of the aqueous phase separated compared to the emulsions free of MEG, but significantly delayed the demulsification process. Rheology provided important information regarding the phase separation process of the aqueous phase in oil phase emulsions, and dynamic testing suggested that the most relevant effect of the addition of MEG is an increase of the emulsion elasticity that can be correlated with the increase in the emulsion stability observed by bottle test and Turbiscan.