Thiourethane-based thiol-ene (TUTE) films were prepared from diisocyanates, tetrafunctional thiols and trienes. The incorporation of thiourethane linkages into the thiol-ene networks results in TUTE films with high glass transition temperatures. Increases of T g were achieved by aging at room temperature and annealing the UV cured films at 85 8C. The aged/annealed film with thiol prepared from isophorone diisocyanate and cured with a 10,080-mJ/cm 2 radiant exposure had the highest DMA-based glass transition temperature (108 8C) and a tan d peak with a full width at half maximum (FWHM) of 22 8C, indicating a very uniform matrix structure. All of the initially prepared TUTE films exhibited good physical and mechanical properties based on pencil hardness, pendulum hardness, impact, and bending tests. V V C 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5103-5111, 2007