A series of novel crosslinked poly(urethane-methacrylate) (PUA) was synthesized. PUA was polymerized in three-step process: The low number average molecular weight unsaturated polyester (UPE) containing hydroxyl groups was synthesized by 1,2-propanediol (PG), 2-butyl-2-ethyl-1,3-propanediol (BEPD) and maleic anhydride (MA). A series of prepolymers, which had double bonds at the end of the chain, was prepared from isophorone diisocyanate (IPDI), UPE, and beta-hydroxyethyl methacrylate (HEMA) hi the presence of dibutytin dilaurate (DBTL) as catalyst. The novel functional prepolymer was initiated by 2,2-azobis-isobutyronitrile(AIBN) to form thermosetting materials. The structure of the thermosetting materials was characterized by Fourier Transform Infrared (FTIR). Mechanical, thermal, and optical properties were tested. The results showed that the advanced PUA had good thermal and mechanical properties and high transparence. The throughput of PUA was above 90%, thus the PUA was possible to be used as excellent optical material. (C) 2008 Wiley Periodicals, Inc. J Appl Polym Sci 111: 724-729, 2009