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.