Impossible voltage plateau regulation for the cathode materials with fixed active elemental center is a pressing issue hindering the development of Na-superionic-conductor (NASICON)-type Na3 V2 (PO4 )2 F3 (NVPF) cathodes in sodium-ion batteries (SIBs). Herein, a high-entropy substitution strategy, to alter the detailed crystal structure of NVPF without changing the central active V atom, is pioneeringly utilized, achieving simultaneous electronic conductivity enhancement and diffusion barrier reduction for Na+ , according to theoretical calculations. The as-prepared carbon-free high-entropy Na3 V1.9 (Ca,Mg,Al,Cr,Mn)0.1 (PO4 )2 F3 (HE-NVPF) cathode can deliver higher mean voltage of 3.81 V and more advantageous energy density up to 445.5 Wh kg-1 , which is attributed by the diverse transition-metal elemental substitution in high-entropy crystalline. More importantly, high-entropy introduction can help realize disordered rearrangement of Na+ at Na(2) active sites, thereby to refrain from unfavorable discharging behaviors at low-voltage region, further lifting up the mean working voltage to realize a full Na-ion storage at the high voltage plateau. Coupling with a hard carbon (HC) anode, HE-NVPF//HC SIB full cells can deliver high specific energy density of 326.8 Wh kg-1 at 5 C with the power density of 2178.9 W kg-1 . This route means the unlikely potential regulation in NASICON-type crystal with unchangeable active center becomes possible, inspiring new ideas on elevating the mean working voltage for SIB cathodes.