Unveiling the ion transport mechanism to design and explore efficient and stable ion transport pathways for high‐performance transition metal oxide (TMO)−based electrochromic materials is highly desired yet challenging. Herein, this study has demonstrated that the interlayer spacing of layered vanadium penoxide (V2O5) films can be tuned by inserting different amounts of lithium−ion (Li+) within host V2O5 material, as well as adjusting ion transport behavior and electrochromic performance. These results show that V2O5 with a small amount of ion insertion delivers a stable ion transport process and electrochromic properties. Increasing the amount of inserted Li+ will enlarge the interlayer spacing, which provides abundant active sites and efficient ion transport channels, and thus reversible and rich color variation of yellow−green−blue−olive green−orange is realized. Nevertheless, an excess of ion insertion results in the crystal structure collapse and cyclic stability degradation. These findings give a rationale for the evolution of electrochromic properties during different electrochemical reaction stages. This work provides considerable insight into the ion transport behavior within the layered V2O5 films, which gives fundamental theoretical guidance for developing and designing superior layered TMO electrochromic materials.