Herein, we propel 3D printable liquid crystalline shape memory materials from solely elastomeric performance to the thermomechanical performance of tough, yielding thermosets by utilizing Hot Lithography, which allows light-based printing at temperatures up to 140 °C. For this purpose, we have designed a mesogenic terminal alkene monomer to achieve a broad temperature range of the LC phase, which is stable even in the presence of non-LC thiol comonomers (Figure ). The LC phase stability of this monomer is screened in combination with a variety of trifunctional thiol comonomers, which vary in molecular weight and rigidity. Furthermore, the liquid crystalline behavior before polymerization and the thermomechanical behavior after polymerization is characterized. To confirm the hypothesized structure-property relationships, we elucidate the microstructure of the most crystalline materials. Finally, we successfully demonstrate shape-memory behavior and 3D printing for one monomer combination.