The effects of (NH4)2Sx treatment on the current-voltage characteristics and interfacial properties of the indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene) doped with poly(4-styrenesulfonate) (PEDOT-PSS) samples have been investigated in this study. The authors found that (NH4)2Sx treatment could lead to the improvement of the interfacial stability of ITO/PEDOT-PSS samples. In addition, the current transport at the ITO/PEDOT-PSS interface is governed by the defects induced by interfacial reactions.