2-Nonyl-2-oxazoline and 2-(9-decenyl)-2-oxazoline have been copolymerized in different proportions by cationic ring-opening polymerization to obtain a series of random linear copolymers with tailored molecular weight and double bond functionality in the side chains. Thiol-ene addition of 2-mercaptoethanol has been used to produce a set of polyoxazoline-polyols under mild conditions and with quantitative double bond transformation. The polyols obtained in this way were reacted with methylene-bis(phenylisocyanate) to yield a series of amorphous and semicrystalline polyurethane networks. The thermal stability and the thermomechanical properties of these thermosets have been studied and related with the structure of the parent polyols. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 3069-3079, 2011