We first compare different types of hydrogels (two generated via thiol-ene coupling and one conventional acrylate gel) prior to the investigation of thiol-ene silicone, in comparison with a commercial silicone, Sylgard. We examine in particular the toughness and failure behaviour of these samples. Finally, we investigate the mechanics and failure properties of a propargylated polyester (PCL) bonded to a thiol-ene gel via direct coupling between thiol residues of the hydrogel matrix to alkynes side chains of the modified PCL. This study demonstrates the strong bonding achieved by thiol-ene coupling, and associated toughness, in particular when bonding hydrogel and elastomeric phases both relying on this chemistry.