Liquid-crystalline thermosets (LCTs) were prepared by the curing of difunctional liquid-crystalline dimeric epoxy monomers with imine moieties in the mesogenic core and central spacers of different lengths. Tertiary amines were used as catalysts in different proportions. The locked mesophases of the LCTs were characterized by polarized optical microscopy and wide-angle X-ray scattering and identified as smectic-C, regardless of their smectic-A or smectic-C initial state. The influence of a 7.1-T magnetic field on the macroscopic orientation of these materials was studied by dynamic mechanical analysis, and the orientation parameter was determined by IR dichroism.