The glycidyl (Gly)-terminated liquid crytalline (LC) monomer GlyOPhC(Me)=CHPhOGly is cured with aromatic amines. A nematic structure suddenly develops during the curing reaction and is related to the molecular weight increase of the developing network. An unusual exothermal double peak is observed in the isothermal curves obtained in a defined temperature range. The calorimetric analysis is used to evaluate the kinetic parameters and is related to the initial formation of a linear prepolymer and to the subsequent development of the tridimensional network