The incorporation of vitrimer bond-exchange chemistry into liquid crystalline elastomer networks produces ‘exchangeable liquid crystal elastomers’ (xLCE). These materials offer a facile method of material re-shaping and alignment post-polymerisation via the application of a mechanical stress above the temperature of activation of bond exchange. We use di-epoxy mesogenic monomers with thiol-terminated spacers and crosslinker to investigate a range of resulting xLCE. The “click” chemistry of thiols results in good control over the network topology, and low glass transition in this family of materi-als. By combining different spacers, we were able to obtain smectic and nematic phases, and adjust the liquid crystal to iso-tropic phase transition between 42 and 140 °C, while the elastic-plastic transition temperature was maintained close to 200 °C. The broad gap between these temperatures ensures that thermally actuating uniformly aligned elastomers are stable and show no residual plastic creep, making epoxy-thiol xLCE promising for a range of engineering applications.ERC H202
