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The impacts of Cu substitution upon the cycling stability of Na x MO 2 (M = Fe, Mn) cathodes are systematically studied. Evidenced by CuO segregation and XPS analysis, the average valence of Mn can hardly reach +4, possibly owing to the production of Mn(II). It is proposed that, Cu substitution can efficiently enhance the cycling stability by reducing the content of Mn(III) and suppressing the electrochemical activities of Mn4+/3+ redox couple. • Cycling stability of Na x MO 2 (M = Cu, Fe, Mn) cathodes are systematically studied. • CuO segregation is evidenced to be associated with the limited valent state of Mn. • Adding Cu2+ actually lower Mn valence by decreasing Mn(III) and generating Mn(II). • Cu2+-substitution may enhance the cycling stability mainly by suppressing Mn(III). Adding Cu2+ has substantially boosted the practical potentiality of Fe/Mn-based layered cathodes for sodium ion batteries (SIBs) owing to the enhanced stabilities, which were previously ascribed to the raised valence of Mn. Herein, the roles of Cu2+ are verified by investigating Cu2+-substituted materials with the stoichiometry of Na 0.5+x Cu x Fe 0.5-x Mn(IV) 0.5 O 2. Surprisingly, it is found that Mn valence can hardly reach the expected value (IV) even by adjusting Cu2+ content. For the first time, the separation of CuO, which has been previously detected but rarely explained, is ascribed to the restrained chemical states of Mn. Detailed analyses show that, Mn(II) is generated while Mn(III) is decreased in pace of Cu2+ substitution, actually lowering down the oxidation states of Mn. Moreover, Mn4+/3+ redox can be efficiently restricted by importing Cu2+. Albeit the loss of capacity, the cycling stability is greatly enhanced, achieving a high capacity retention of 92.3% after 200 cycles within 4.2–2.5 V. Therefore, the suppression of Jahn-Teller Mn(III) should be intrinsically responsible for the superior cycling stability after Cu2+ substitution. These findings may present a new sight to probe the roles of Cu in layered Na x MO 2 system for the design of advanced cathodes for SIBs. [ABSTRACT FROM AUTHOR]