The sodium superionic conductor (NASICON) suffer from irreversible phase transition and insufficient cycle life above 4 V. Innovations in high-performance NASICON cathodes, alongside the comprehension of their corresponding structural and chemical aspects, remain a challenge. Inspired by the high-entropy alloys, this work proposes a NASICON cathode structure, Na4Cr0.7Fe0.4Mn0.3V0.3Al0.2(PO4)3 (HE-NASICON). HE-NASICON exhibits a reversible capacity of 165.0 mAh g−1 at 0.1 C. It undergoes successive oxidation–reduction reactions, enabling high-voltage multi-electron reactions. Furthermore, HE-NASICON maintains a capacity retention of 70.5 % after 2,000 cycles at 10 C (1.2 A g−1). In-situ X-ray diffraction analysis revealed minimal volume variation of HE-NASICON cathode crystals (1.45 %), indicating excellent stability, with the effective resistance of adverse crystal evolution by the high-entropy stabilization effect (ΔSconf >1.5R). Forming a full cell with hard carbon as the anode, it delivers a cathode-based specific capacity of 131.09 mAh g−1 at 12 mA g−1, achieving an energy density of 307.06 Wh kg−1. Considering the commercialization of NASICON-type cathodes necessitates higher energy density and lower costs. HE-NASICON not only significantly reduces the use of vanadium, thus lowering battery costs, but also anticipates widespread application of this strategy for enhancing positive electrode configuration entropy in the development of polyanion electrode materials.