The influence of thermal history on the formation of HECA liquid crystalline phase was studied by DSC. It was found that the degree of ordering in the liquid crystalline phase was heterogeneous, and the multiphase transformation appears when the liquid crystalline phase transformed to the isotropic one. When HECA was annealed in the liquid crystalline state, the parts with the lower degree of ordering could transform to ones with the higher degree of ordering, and the temperature and the enthalpy of the phase transformation from the liquid crystalline phase to the isotropic phase increased.