Vanadium pentoxide (V₂O₅) delivers a highly reversible specific capacity of 294 mAh/g corresponding to two Li ions inserted into the host layered spaces. More attention, in the past decades, has been focused on the cycling stability and capacity enhancement through microstructure design and surface modification and layer spacing regulation. However, the change on the discharging voltage of vanadium pentoxide was ignored, especially, the remarkable increase happens in the first cycles. Herein, the phase structures and the chemical bonds of V₂O₅ were monitored by X-ray diffractometer and Raman spectroscopy at different charging/discharging states. The recorded patterns revealed the irreversible phase transition stemmed from γ-LixV₂O₅ that was partially transformed to γ’ -V₂O₅ rather than the completely pristine α-V₂O₅. The coexisted phases mutually changed their bond lengths that induced the changes on crystal field and electron cloud distribution, resulting in the decrease of electrons energy level in 3d orbitals and site energy for Li ion occupation. The revealed relationship between electrochemical potential and phase structures can provide a new sight to study and design high-voltage cathode that makes sure the possible full battery with a higher energy density.