Metal ion‐enzyme tandem systems hold immense potential for biocatalysis, environmental remediation, and medical therapy, yet their development is hindered by inherent incompatibility, low ion concentration, and spatial distance barriers between metal ions and enzyme, limiting the maximization of metal ion catalytic potential. Here, we developed a convenient one‐step doping strategy to achieve spatial separation of high concentration metal ions and enzymes within single metal‐organic frameworks (MOFs). Catalytically active metal ions partially replace MOF sites through ligand coordination, while enzymes are in‐situ encapsulated (enzyme@M‐MOFs), maintaining structural integrity and enhancing stability. This design enables efficient chem‐bio tandem reactions by preventing mutual inactivation and accelerating reaction rates due to distance shortening between metal ions and enzymes. The enzyme@M‐MOFs exhibit good therapeutic effect in diabetic wound healing, establishing a new paradigm for catalytic medicine applications. The strategy's versatility is demonstrated by its successful application with a range of metal ions (Fe²⁺, Mg²⁺, Cd²⁺ …) as catalysts or enzyme promoters. By transforming incompatible systems into compatible tandem platforms, this work offers a universal approach for efficient chemical‐enzyme tandem catalysis, unlocking novel possibilities in biocatalysis and beyond.

Carbonaceous materials are promising anode candidates for potassium-ion batteries (PIBs) given its high conductivity, stable property, and abundant resource, while its practical implementation is still hampered by its limited capacity and inferior rate behavior. Herein, we report a superior carbonaceous anode through a combined strategy of carbon hybridization and heteroatom doping. In this composite, hollow carbon spindles (HCS) were anchored on the surface of graphene (G) followed with sulfur doping treatment, aiming to integrate the high conductivity of graphene, the good structure stability of HCS, and the S doping-induced ample active sites. As a PIB anode, the S-G@HCS composite can display high capacity (301 mA h g⁻¹ at 0.1 A g⁻¹ after 500 cycles) and long-term cyclability up to 1800 cycles at 2 A g⁻¹. Impressively, it can deliver an outstanding rate capacity of 215 mA h g⁻¹ at 10 A g⁻¹, which is superior to most carbon anodes as-reported so far for PIBs. Experimental and theoretical analysis manifests that the construction of graphene/amorphous carbon interface as well as S doping enables the regulation of electronic structure and ion adsorption/transportation properties of carbonaceous material, thus accounting for the high capacity and superior rate capability of S-G@HCS composite.