To understand the electrochemical capacity fading of the polyaniline (PANI) electrodes in supercapacitors, for the first time, their chemical structure change during electrochemical cycles was traced with XPS analysis after the HCl doped PANI electrodes were subjected to the cyclic voltammetry test in 1.0 M H₂SO₄ electrolyte for different cycle numbers. The results showed that the chlorine disappeared in the electrode surface, while the surface element contents of sulfur and oxygen increased with the electrochemical cycles increased. It demonstrated that the hydrolytic degradation of the PANI chains and exchange of dopant occurred during the electrochemical cycling, causing the fading in the mechanical and electrochemical performance of the PANI electrodes. This understanding should lead to better design of the conductive polymer-based energy storage devices.