This work introduces a new paradigm— “guest‑binding counterion cluster gating”. Unlike classical gating (ligand rotation, framework breathing, or single‑ion movement), an entire tetrahedral ion cluster undergoes selective bond reconstitution and cooperative deformation, acting as an active, guest‑responsive gate. The ability to produce battery‑grade DMC (>99.9999%) from an azeotrope in a single ambient step, combined with kilogram‑scale synthesis (92.6% yield) and excellent cycling stability, suggests immediate industrial potential. In summary, this MOF breaks the MeOH/DMC azeotrope with far lower energy (1.10 vs. >10 MJ kg^-1 MeOH), meeting the battery industry's demand for ultra‑high purity DMC. Moreover, the mechanistic insights open a new dimension for designing next‑generation molecular sieves: by tuning the size, charge, and coordination flexibility of counterion clusters, other challenging azeotropic or close‑boiling mixtures could be separated.