We report a simple, serendipitous, two step mediation that overcomes the polyaddition threshold of castor oil during polyurethane formation. The mediation facilitates formation of polyurethane systems directly from castor oil without triricinolein chain extension or the use of supplementary hydroxyl compounds. The mediation involves refluxing castor oil with n-Butyl lithium in the presence of a solvent followed by water addition. We demonstrate the effectiveness of this mediation by successfully generating two important polyurethane systems (foam and coating) from castor oil. We identify that the mediation introduces two new compounds in castor oil namely, a lithiated diglyceride and a lithium salt of fatty acid. We characterize the new polyurethane synthesized for their hard-soft segmented morphology, glass transition temperature, and thermomechanical properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43964. © 2016 Wiley Periodicals, Inc.