A new series of liquid-crystalline epoxy resins was synthesized, and their mesomorphic behavior was investigated with differential scanning calorimetry, polarized optical microscopy, and wide-angle X-ray scattering. These glycidylic compounds had central aromatic imine mesogens derived from benzidine and aliphatic spacers of up to 10 methylene units that linked the mesogens to the glycidylic groups. Crosslinking these monomers with primary aromatic diamines led to nematic networks, some of which contained crystal inclusions. However, through curing with tertiary amines as catalytic agents or through copolymerization with different proportions of the nonmesomorphic epoxy monomer and primary amines as crosslinking agents, smectic C organized thermosets were prepared when the spacers had at least four methylene carbons. When they had fewer than four, the networks were nematic. (C) 2004 Wiley Periodicals, Inc.