In this study, we conducted the first energy dispersive x-ray diffraction (EDXRD) experiments on Li/Li1.1V3O8 coin cells discharged to different lithiation levels in order to investigate the phase transitions upon electrochemical reduction. The phase transformation from layered Li-poor α to Li-rich α to defect rock-salt β phase was confirmed with cells of different lithiation stages. No spatial localization of phase formation was observed throughout the cathodes under the conditions of this measurement.