Abstract: The present invention is related to an improved process for obtaining oleochemical polyols from oils, principally of a vegetable origin. The polyols obtained consist of a mixture of ethers, esters, primary and secondary alcohols and have the characteristic of being self-compatible with the new blowing agents: hydrochlorofluorocarbons, HCFC's, hydrofluorocarbons, HFC's and hydrocarbons, HC's of a low molecular weight and low boiling point. The process of this invention is characterized because it uses Lewis type acids in such a way that they do not form precipitates and therefore it is not necessary to remove precipitates from the polyol. The process of the present invention makes it possible to obtain polyols with high functionality and controlled reactivity. These characteristics render the product suitable for use as a raw material in the production process of rigid foams, such as polyurethane for spraying, refrigeration and imitation wood, coatings, among others.