Highly safe lithium-ion batteries (LIBs) are required for large-scale applications such as electrical vehicles and energy storage systems. A highly stable cathode is essential for the development of safe LIBs. LiFePO₄ is one of the most stable cathodes because of its stable structure and strong bonding between P and O. However, it has a lower energy density than lithium transition metal oxides. To investigate the high energy density of phosphate materials, vanadium phosphates were investigated. Vanadium enables multiple redox reactions as well as high redox potentials. LiVPO₄O has two redox reactions (V⁵⁺/V⁴⁺/V³⁺) but low electrochemical activity. In this study, LiVPO₄O is doped with fluorine to improve its electrochemical activity and increase its operational redox potential. With increasing fluorine content in LiVPO₄O_1-xF_x, the local vanadium structure changed as the vanadium oxidation state changed. In addition, the operating potential increased with increasing fluorine content. Thus, it was confirmed that fluorine doping leads to a strong inductive effect and high operating voltage, which helps improve the energy density of the cathode materials.