UV-induced thiol-ene crosslinked films composed of linear methacrylate copolymers having pendant enes (MCPenes) are reported. An approach involving a combination of controlled radical polymerization to synthesize well-controlled pendant hydroxyl containing copolymers (MCP(OH)s) with the following facile carbodiimide coupling of the formed MCP(OH)s with enes allows for the synthesis of well-controlled MCPenes with narrow molecular weight distribution. The density of the pendant enes in MCPenes are easily modulated by varying monomer ratios in the feed. Under UV irradiation, the resulting MCPenes undergo thiol-ene polyaddition reactions with polythiols to form crosslinked films with a uniform network. The results from thermal and mechanical analysis suggest these properties are tuned by adjusting the densities of pendant enes in MCPenes and the amount of thiols in the reactive mixtures. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 572-581