Amorphous poly(ethylene terephthalate) (PET) films with different thermal histories were annealed at 30 degrees C in a desiccator, in a humid atmosphere and in liquid water respectively, for investigation of enthalpy relaxation by differential scanning calorimetry (DSC). For the quenched sample annealed in a humid atmosphere, the evolution of the endothermic peak near the glass transition temperature (Tg) with annealing time is remarkable. For the aged samples further annealed in the humid atmosphere and water, the shape of the endothermic peak changed from a single peak into broad double peaks with annealing time. However no such change of the endothermic peak can be observed for both the quenched and the aged samples further annealed in the desiccator. The experimental results showed that the change of the DSC curve was reversible, involved only with the physical process. The results may indicate that some ordered structure formed during the physical ageing process.