Oleic acid is a typical unsaturated fatty acid that is found widely in vegetable oils. The objective of this investigation was to produce a new type of oleic-based polyol from oleic acid. Possible advantages of this approach include the production of high-performance polyurethane materials from renewable resources and value-added research for oleic acid. Oleic-based polyols were synthesized by a three-step process consisting of epoxidation and ring-opening reaction, followed by esterification. The synthesized polyols appeared as a viscous liquid at room temperature with hydroxyl numbers from 307 to 425 mg KOH/g. Preparation of polyurethane foams using oleic-based polyols and isocyanate was studied. An environmentally friendly blowing agent, HCFC-141b, together with a small amount of water, was used. The synthesized foams were characterized by FTIR, SEM, and TG/DSC. (c) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012