Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is usually sandwiched between indium tin oxide (ITO) and a functional polymer in order to improve the performance of the device. However, because of the strong acidic nature of PEDOT:PSS, the instability of ITO/PEDOT:PSS interface is also observed. The mechanism of degradation of the device remains is unclear and needs to be further studied. In this article, we investigate the in-situ electrochromism of PEDOT:PSS to disclose the cause of the degradation. X-ray photoelectron spectroscopy (XPS) was used to characterize the PEDOT:PSS films, as well as the PEDOT:PSS plus polyethylene glycol (PEG) films with and without indium ions. The electrochromic devices (ECD) based on PEDOT:PSS and PEG with and without indium ions are carried out by in-situ micro-Raman and laser reflective measurement (LRM). For comparison, ECD based on PEDOT:PSS and PEG films with LiCl, KCl, NaCl or InCl3 are also investigated by LRM. The results show that PEDOT:PSS is further reduced when negatively biased, and oxidized when positively biased. This could identify that PEDOT:PSS with indium ions from PEDOT:PSS etching ITO will lose dopants when negatively biased. The LRM shows that the device with indium ions has a stronger effect on the reduction property of PEDOT:PSS-PEG film than the device without indium ions. The contrast of the former device is 44%, that of the latter device is about 3%. The LRM also shows that the contrasts of the device based on PEDOT:PSS+PEG with LiCl, KCl, NaCl, InCl3 are 30%, 27%, 15%, and 18%, respectively.