Powders of HCl protonated polyaniline (HCl-PAni) and films of camphor sulfonic acid protonated polyaniline (CSA-PAni) were heated at constant temperature in air. The different samples have been studied by X-ray diffraction analysis in order to characterize the effect of aging procedure on the crystalline structure of these materials. A monotonic transition between two phases can characterize the structural evolution of HCl-PAni powdered samples. By contrast, the structure of the CSA-PAni films is evolving through several steps as a function of the aging time.