The monotropic nematic diglycidylether of 4-hydroxyphenyl-4’-hydroxybenzoate was crosslinked in the isotropic and in the nematic states using alpha,alpha’-dimethoxydeoxybenzoin and diphenyliodoniumhexafluorophosphate as the photoinitiator system. The glass transition temperature of networks synthesized in the liquid-crystalline state is higher than in the isotropic state. Networks with ordered structures show a second transition state at a lower temperature. Both these transition temperatures can be contributed to phase separation during network formation. Furthermore, two different ordered structures were detected by polarization microscopy in networks synthesized by photoinduced crosslinking of 4-hydroxyphenyl-4’-hydroxybenzoate containing a small amount of the diglycidylether of 1,4-phenylene-bis-4’-hydroxybenzoate. The frozen ordered structures possess a high thermal stability.