Triggering the anionic redox chemistry in layered oxide cathodes has emerged as a paradigmatic approach to efficaciously boost the energy density of sodium-ion batteries. However, their practical applications are still plagued by irreversible lattice oxygen release and deleterious structure distortion. Herein, a novel P2-Na 0.76 Ca 0.05 [Ni 0.23 □ 0.08 Mn 0.69 ]O 2 cathode material featuring joint cationic and anionic redox activities, where native vacancies are produced in the transition-metal (TM) layers and Ca ions are riveted in the Na layers, is developed. Random vacancies in the TM sites induce the emergence of nonbonding O 2p orbitals to activate anionic redox, which is confirmed by systematic electrochemical measurements, ex situ X-ray photoelectron spectroscopy, in situ X-ray diffraction, and density functional theory computations. Benefiting from the pinned Ca ions in the Na sites, a robust layered structure with the suppressed P2-O2 phase transition and enhanced anionic redox reversibility upon charge/discharge is achieved. Therefore, the electrode displays exceptional rate capability (153.9 mA h g −1 at 0.1 C with 74.6 mA h g −1 at 20 C) and improved cycling life (87.1% capacity retention at 0.1 C after 50 cycles). This study provides new opportunities for designing high-energydensity and high-stability layered sodium oxide cathodes by tuning local chemical environments.