The effect of inert coating materials such as Nafion on the non-lithiated LiV3O8 cathode of lithium-metal rechargeable batteries was studied. This uniform and thin coating layer was deposited using electrostatic spray deposition to suppress the crack formation caused by volume expansion and prevent the dissolution of vanadium in the electrolyte. The Nafion coated LiV3O8 electrode exhibited a higher discharge capacity and better capacity retention after 200 cycles (150.86 mAh g(-1) and 62.9%, respectively) than the bare LiV3O8 electrode (113.31 mAh g(-1) and 46.8%, respectively). The Nafion coated LiV3O8 electrode was characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, and inductively coupled plasma mass spectrometry. Its electrochemical performance was analyzed using a battery testing system and impedance spectroscopy. Our findings show that the inert coating layer on the LiV3O8 cathode plays an important role in improving its electrochemical performance.