Spinel LiMn2O4 (LMO) renders as a prevailing cathode material for lithium-ion batteries (LIBs) in prospect of its cost-effectiveness, nontoxicity and high energy density. Nevertheless, the LMO is inevitably confronted with sluggish diffusion kinetics and drastic capacity degradation triggered by multiple issues, including Jahn-Teller distortion, Mn dissolution and structural attenuation. Thereinto, a metal-organic framework (MOF) chemistry engineering for hierarchical micro-/nano-structural F, O-dual-doped carbon embedded oxygen vacancy enriched LiMn2O4 cathode (OV-LMO@FOC) is proposed for LIBs. Bestowed by experimental and theoretical implementations, systematic investigations of OV-LMO@FOC endow that the meticulous integration of F, O-dual-doped carbon and oxygen vacancy in LMO-based cathode reconfigures the electronic structure, boosts electronic conductivity, expedites diffusion capability, facilitates energetically preferable Li+ adsorption, and suppresses Mn dissolution. As expected, the OV-LMO@FOC behaves with compelling electrochemical performance with prosperous specific capacity (130.2 mAh g−1 at 0.2 C upon 200 loops), exceptional rate capacity (93.7 mAh g−1 at 20 C), and pronounced long-term cyclability (112.5 mAh g−1 after 1200 loops with 77.6% capacity retention at 1 C; 96.9 mAh g−1 upon 1000 loops with 90.7% capacity retention at 5 C). This work envisions the MOF-chemistry in surface modification and electronic modulation engineering of high-performance materials towards industrialization in automotive market.