Overall, the bonding of thiol-ene hydrogels to thiol-ene and thiol-yne elastomers and hydrophobic matrices appear particularly strong and seems to be limited by the surface density of reactive residues, in the absence of strong interpenetration of the two networks. Indeed, little infiltration of the gel network is expected into the PCL phase of propargylated PCL, owing to its relatively high glass transition and crystallinity, compared to silicones, and melting temperature. Another interesting feature of thiol-ene chemistry for design of hybrid structures is the relative insensitivity of this chemistry to oxygen concentrations, therefore limiting variations in apparent moduli that are observed in conventional radical polymerisation-based hydrogels. The sensitivity of the ultimate tensile stress on the chemistry of the interface, even in the absence of marked changes in apparent Young's modulus remains unclear, but we suggest it could arise from changes in ultimate strains at break observed, possibly reflecting slight changes in network formation and associated energy dissipation, or potentially highlighting partial network interpenetration at interfaces. In any case, our data clearly indicates that thiol-ene coupling at the interface of hybrid constructs offers great opportunities of design in corresponding multiphase elastomer-hydrogel structures, generated from microfabrication or 3D printing platforms.