Phase engineering has been efficiently employed to improve the performance of transition metal oxide cathode materials by alleviating the Jahn-Teller effects and optimizing the ions diffusion pathway. The second-order Jahn-Teller effects by slight molybdenum substitution was confirmed to activate a new phase formation and to construct a multiphase riveting structure. A P3/O3 riveting-structured NaNi0.3Mn0.52Mo0.03Cu0.1Ti0.05O2 cathode material was successfully synthesized for sodium ion batteries, which undergoes a reversible phase transition from P3/O3 → P3 → Hex.O3′ when charged to 4.25 V and most of the materials will transform into P3 phase after the first charge–discharge cycle. Due to the high reversibility and crystal structure stability, it indicates 155.0 mAh g−1 discharge capacity with a high up to 99.65 % initial Coulomb efficiency. This P3/O3 riveting structure can alleviate the rigid failure caused by phase transition. Meanwhile, O3/P3 phases provide the main storage sites for Na+ as skeletons and the existence of P3 phase provides a better diffusion pathway for ion transport.