The lack of suitable high-voltage cathode materials has hindered the development of rechargeable magnesium batteries (RMBs). Here, mesoporous Na3 V2 (PO4)3 /C (NVP/C) spheres have been synthesized through a facile spray-drying-annealing method, and their electrochemically desodiated phase NaV2 (PO4)3 /C (ED-NVP/C) has been investigated as an intercalation host for Mg2+ ions. The obtained ED-NVP/C exhibits an average discharge voltage of around 2.5 V (vs. Mg2+ /Mg), higher than those of most previously reported cathode materials. In addition, it can deliver an initial discharge capacity of 88.8 mA h g-1 at 20 mA g-1 , with good cycling stability. Ex situ X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results demonstrate that the electrochemical reaction is based on an intercalation mechanism and shows good reversibility. Galvanostatic intermittent titration technique (GITT) data have revealed that the intercalation process involves a two-phase transition. The reported ED-NVP/C cathode material with high working voltage offers promising potential for application in RMBs.