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MOF-derived XMn 2 O 4 (X = Zn, Co, Cu, Ni) nanomaterials achieve superior electrochemical performance for lithium storage. [Display omitted] • Two methods are proposed for the synthesis of XMn 2 O 4 (X = Zn, Co, Cu, Ni). • MOF-derived anodes exhibit excellent electrochemical capabilities compared with the ones obtained by simple coprecipitation. • Lithium storage capacity and rate performance of XMn 2 O 4 is best when X = Zn. • DFT calculations are performed to demonstrate that ZnMn 2 O 4 as an anode material is conducive to the diffusion of Li+. Bimetallic spinel transition metal oxides play a major part in actualizing eco-friendly electrochemical energy storage systems (ESSs). However, structural precariousness and low electrochemical capacitance restrict their actual implementation in lithium-ion batteries (LIBs). To address these demerits, the sacrificial template approach has been considered as a prospective way to strengthen electrochemical stability and rate performance. Herein, metal-organic frameworks (MOFs) derived XMn 2 O 4 -BDC (H 2 BDC = 1,4-dicarboxybenzene, X = Zn, Co, Cu, Ni) are prepared by a hydrothermal approach in order to discover the effects of various metal cations on the electrochemical performance. Among them, ZnMn 2 O 4 -BDC displays best electrochemical properties (1321.5 mAh g−1 at the current density of 0.1 A g−1 after 300 cycles) and high efficiency with accelerated Li+ diffusivity. Density functional theory (DFT) calculations confirm the ZnMn 2 O 4 possesses the weakest adsorption energy on Li+ with a minimized value of −0.92 eV. In comparison with other XMn 2 O 4 through traditional fabrication method, MOF-derived XMn 2 O 4 -BDC possesses a higher number of Li+ transport channels and better electric conductivity. This tactic provides a feasible and effective method for preparing bimetallic transition metal oxides and enhances energy storage applications. [ABSTRACT FROM AUTHOR]