Tuning the comonomer molecular weight to achieve liquid crystalline preordering enhances the polymer crystallinity and crosslink density, which are typically competing properties. Further comonomer adjustment allows the programming of mechanical properties from those of a stiff, hard thermoset to those of a tough, yielding thermoplastic with over 200% elongation. Micro-and nanostructural analysis indicate phase separation between soft and hard phases as a result of the liquid crystalline preordering, effectively acting as a thermomechanical toughening mechanism. Lastly, we demonstrate 3D printing of one of these materials using the Hot Lithography method, and its potential as a functional, smart material that additionally displays shape memory behavior with a shape imprinting response of over 99% fixity and shape recovery values of above 98% over numerous cycles after an initial acclimatization phase. The high shape recovery temperature enables a broad application temperature range (0-100°C) without unintended shape recovery.