AbstractA novel process for the industrial production of hydroxylated fatty acids involves epoxidation of plant oils and their derivatives, followed by catalytic epoxy ring opening in the presence of water or other hydrogen donors, such as alcohols, diols, and amines. Depending on the starting material, epoxidation followed by opening of the oxirane ring leads to fatty acids that contain vicinal diol groups or to other substituted hydroxylated fatty acid derivatives. As an example for the preparation of a substituted hydroxylated fatty acid derivative, the reaction of epoxidized rapeseed oil with monobutylamine as hydrogen donor is described. Apart from the intended formation of hydroxyl groups with vicinal aminoalkyl groups, partial aminolysis of the ester compound was also observed. Another example describes the reaction of epoxidized rapeseed oil with different molar proportions of 1,4‐butanediol as hydrogen donor. Depending on the molar proportion of the hydrogen donor, interesterification, or intermolecular ether formation were observed as side reactions. The properties of various technical hydroxylated fatty acids and their derivatives, prepared according to this novel process, are given, and potential applications of these products are suggested.