The newly synthesized monomer was copolymerized with four different trifunctional thiol comonomers in photoreactive formulations (Figure ), in which equal amounts of thiol and alkene groups were employed. To improve crystallinity, the mesogen load was maximized by avoiding dithiol chain extenders. Their liquid crystalline phase behavior was assessed on a polarized optical microscope and revealed a strong correlation of the weight fraction of LCM with the presence and stability of an LC phase (Figure ). At nearly equal weight fractions of LCM and thiol in formulations containing 100% of the high-molecular weight comonomer ETTMP, no LC phase is observed. Mixtures of LCM with the comonomer TEMPIC increase the LCM weight fraction only slightly, hence an isotropic melt occurs across all temperature ranges, except for traces of liquid crystallinity close to the recrystallization temperature during cooling. The formulation containing TMPMP as comonomer displays a partial LC phase (less than 50% of the observed area covered by liquid crystalline regions, in the shape of small droplets), which persists for 25 °C above the melting point. From LCM weight fractions of at least 65% on, distinct LC phases dominate across large areas of the formulation, which is the case for the lowmolecular weight crosslinker CHTT. To vary the crosslinking density, the flexible toughener ETTMP was added as substituent for CHTT in concentrations of 10 and 20 mol%, which did not cause a significant change of LC behavior. A stable LC phase across a temperature range of around 10 °C is formed by all three formulations, which gradually reduces in intensity before turning into a fully isotropic melt approximately 30 °C above the melting point. The exact weight fractions and phase transition temperatures are listed in the supplementary information (Supplementary Figure , Supplementary Table ). Therein, all recorded temperatures are subject to some interpretation (± 2-3 °C) as substance mixtures lead to more diffuse phase transitions compared to pure compounds.