Here, by using atomically resolved scanning transmission electron microscopy and electron energy loss spectroscopy, we investigate the structural and chemical evolution of Li₃V₂(PO₄)₃ (LVP) upon the high-voltage window (3.0–4.8 V). We find that the valence of vanadium gradually increases towards the core corresponding to the formation of electrochemically inactive Li_3-xV₂(PO₄)₃ (L_3-xVP) phases. These Li-deficient phases exhibit structure distortion with superstructure stripes, likely caused by the migration of the vanadium, which can slow down the lithium ion diffusion or even block the diffusion channels. Such kinetic limitations lead to the formation of Li-deficient phase along with capacity loss. Thus, the LVP continuously losses of electrochemical activity and Li-deficient phases gradually grow from the particle core towards the surface during cycling. After 500 cycles, the thickness of active LVP layer decreases to be ~ 5–20 nm. Moreover, the micromorphology and chemical composition of solid electrolyte interphase (SEI) have been investigated, indicating the thick SEI film also contributes to the capacity loss. The present work reveals the structural and chemical evolution in the cycled electrode materials at an atomic scale, which is essential to understand the voltage fading and capacity decaying of LVP cathode.