AbstractThe structures of anode materials significantly affect their properties in rechargeable batteries. Material nanosizing and electrode integrity are both beneficial for performance enhancement of batteries, but it is challenging to guarantee optimized nanosizing particles and high structural integrity simultaneously. Herein, a programmable assembly strategy of metal–organic frameworks (MOFs) is used to construct a Sn‐based MOF superstructure precursor. After calcination under inert atmosphere, the as‐fabricated Sn3(PO4)2@phosphorus doped carbon (Sn3(PO4)2@PC‐48) well inherited the morphology of Sn‐MOF superstructure precursor. The resultant new material exhibits appreciable reversible capacity and low capacity degradation for K+storage (144.0 mAh g−1at 5 A g−1with 90.1% capacity retained after 10000 cycles) and Na+storage (202.5 mAh g−1at 5 A g−1with 96.0% capacity retained after 8000 cycles). Detailed characterizations, density functional theory calculations, and finite element analysis simulations reveal that the optimized electronic structure and the stress‐dispersed superstructure morphology of Sn3(PO4)2@PC promote the electronic conductivity, enhance K+/ Na+binding ability and improve the structure stabilization efficiently. This strategy to optimize the structure of anode materials by controlling the MOF growth process offer new dimension to regulate the materials precisely in the energy field.