First-principles calculations combined with density functional theory were performed to illuminate the electrochemical properties of NaVPO4F. During desodiation to VPO4F, a ∼11% volume change was observed, which was ∼2% greater than that from LiVPO4F to VPO4F. An intermediate phase was observed while examining the structural stability during Na+ extraction from NaVPO4F. The voltage profile showed a distinct charging plateau positioned at ∼4.0 V. Bader charge analysis elucidated the reduction of charge-oriented V cations during Na+ extraction. The achieved electron density profiles were examined to analyze the influence of Na+ extraction on V-F and V-O bonds during the desodiation process. The most facile diffusion pathway for Na+ was discerned, with a minimum energy barrier of 0.85 eV. On the basis of these results, NaVPO4F was suggested as a promising cathode material for Na-ion batteries.