The relationship between the chemical structure of liquid crystalline epoxy (LCE) compounds and anisotropic orientation of the crosslinked network was investigated. Three LCE compounds based on aromatic ester mesogenic group were cured with diaminodiphenylester (DDE) under strong magnetic field. Methyl substituent interrupted the orientation of LCE network, while chlorine had little influence on the anisotropic alignment of LCE network. Low coefficient of thermal expansion was observed in the direction of alignment in highly oriented LCE network.