Applied potential plays a significant role in the properties of electrochromic devices (ECDs), for example, cyclic property, optical modulation, and response rate. In this study, inorganic all-solid-state ECDs with the multilayer structure of Glass/ITO/NiOx/Ta2O5/LiNbO3/Ta2O5/WO3/ITO were prepared by magnetron sputtering. The potential dependence of charges dynamic behaviors in the ECDs were analyzed on the basis of cyclic voltammograms (CVs), chronoamperograms (CAs), multi-potential steps, and in-situ optical transmittance at 550 nm. Results demonstrated that the trapping of Li+ ions in NiOx layer and in WO3 layer were responsible for the degradation of electrochromic properties of the ECDs operated at different potential ranges. Besides, the dynamic behavior of Lithorn ions in WO3 layer, acting as the primary electrochromic layer in the ECDs, had a crucial influence on the response characteristics of the ECDs. Excellent optical memory effects at randomly electrochromic extent were observed and the corresponding open-circuit potential was relevant to the chemical potential of the ECDs. (c) 2018 Elsevier Ltd. All rights reserved.