In this study we introduce the use of thiol-ene photopolymers as shape memory polymer systems The thiol-ene polymer networks are compared to a commonly utilized acrylic shape memory polymer and shown to have significantly improved properties for two different thiol-ene based polymer formulations Using thermomechanical and mechanical analysis, we demonstrate that thiol-ene based shape memory polymer systems have comparable thermomechanical properties while also exhibiting a number of advantageous properties due to the thiol-ene polymerization mechanism which results in the formation of a homogeneous polymer network with low shrinkage stress and negligible oxygen inhibition. The resulting thiol-ene shape memory polymer systems are tough and flexible as compared to the acrylic counterparts. The polymers evaluated in this study were engineered to have a glass transition temperature between 30 and 40 degrees C. exhibited free strain recovery of greater than 96% and constrained stress recovery of 100% The thiol-ene polymers exhibited excellent shape fixity and a rapid and distinct shape memory actuation response. (C) 2010 Elsevier Ltd. All rights reserved.