Five azomethine linked triaromatic (triad) mesogenic diepoxides were used to study the phase behaviour during cross-linking anionic polymerization. Clearing points and phase transitions are lowered during polymerization hence, isotropic networks are obtained from noncatalyzed isothermal polymerization. A pronounced influence of the organization of diepoxides in a mesophase on the rate of polymerization was observed for diepoxide 3 which forms a smectic and a nematic mesophase. The reaction rate increases with the smectic/nematic/isotropic transitions of the melt. Increase of the reaction rate with ethyl-methylimidazol (EMI) allows liquid crystalline phases to fix in the resulting network. Organization of anisotropic networks depends on catalyst concentration and curing temperature (reaction rate).