A multi-rate non-isothermal kinetic analysis of the isotropic-melt to liquid crystalline phase transition of novel liquid crystalline ionogenic copolymers, LCIs, the 10-(4-methoxyazobenzene-4′-oxy)decyl methacrylate]-co-2-(acrylamido-2-methyl-1-propanesulfonic acid)s, 10-MeOAzB/AMPS, copolymers, has been performed by means of calorimetric experiments. An analytical methodology which includes the study of the phase transition rate parameter, the determination of the activation energies by using Kissinger and Flynn-Wall-Ozawa models, and the study of the phase transition kinetics by the use of the Avrami theory, has been applied. The formation of the mesophases from the isotropic state occurred close to thermodynamic equilibrium. The results evidence the presence of several individual processes in the formation of liquid crystalline phases from the melt and a strong dependence of phase transition rates and activation energies with acid contents. A decrease in the phase transition rate, related to a decrease in the overall change of the transition entropy, has been observed. The final inhibition of the liquid crystal (LC) behaviour is ascribed to an exponential increase in the activation energy of the phase transition, promoted by strong acid aggregation. An optimum composition of the 10-MeOAzB/AMPS copolymers to achieve the dual characteristics of LCIs (ionogenic and liquid crystalline behaviour) requires acid concentrations capable of promoting structure-forming effects on the LC phases and the evolution of phase separated morphologies.