The goal of this study is to compare the thermal and mechanical properties of a commercial mouthguard material with a novel class of thermoset polymers based on thiolene “click” chemistry. Ternary thiolene systems modified with urethane or acrylate [urethane-modified thiolene network (UMTEN) and acrylate-modified thiolene network (AMTEN), respectively] were synthesized and their properties compared with commercially available Polyshok™. Durometer hardness (ASTM D2240-05), water absorption [ASTM D570-98 (2005)], tear strength (ASTM D624-00), and impact attenuation [ASTM D6110-06f (modified)] were measured for physical property comparison. Differential scanning calorimetry and dynamic mechanical analysis were used as a means to compare thermal properties. One-way analysis of variance and independent t tests were used to test for differences between Polyshok™, AMTEN and UMTEN samples. It was found that the novel thiolene networks exhibit higher impact attenuation at intraoral temperature compared with Polyshok™, although Polyshok™ demonstrates lower water absorption and hardness, as well as higher tear strength. With further modification, this family of thiolene materials may provide a platform for developing next-generation mouthguard materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40402.