The quest for better cathode materials for lithium-ion batteries continues due to its burgeoning application in electric vehicles. In this context, an effort has been made to improve the electrochemical performance of tavorite-structured LiFePO₄F with co-doping of vanadium and sodium ion. A solid-state reaction with FePO₄ and LiF as precursors has been used for the synthesis. Powder X-ray diffraction (XRD) and electron microscopy techniques have been used for product characterization. Addition of dopants leads to a reduction in the particle size of doped LiFePO₄F. The aliovalent substitution of vanadium ion has been ascertained by X-ray photoelectron spectroscopy (XPS). The electrochemical properties have been investigated using charge-discharge testing and electron impedance spectroscopy (EIS). The vanadium- and sodium-doped LiFePO₄F cathodes delivered improved reversible capacities, more stable cycle performance, better rate capability and decreased charge transfer resistance along with enhanced ionic conductivity compared to the pristine sample. The Li_0.95Na_0.05Fe_0.9V_0.1PO₄F cathode delivers a specific capacity of ~100.7 mAh g⁻¹ at a moderate current rate of 1C after an extended run of 2000 cycles with ~94% retention of the initial specific capacity. Sodium addition proves to be beneficial for improving the charge transfer kinetics in the lithium vanadium fluorophosphate–based cathodes for lithium-ion battery.