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UCSB-6 (framework type SBS) and UCSB-10 (SBT), two three-dimensional phosphate-based molecular sieves with supercages accessible through 12-ring (circumscribed by 12 tetrahedral atoms) windows, are structurally similar to the hexagonal and cubic polytypes of faujasite or zeolite Y, an industrially relevant catalyst, but the cage structures are substantially different. Nonetheless, their inherent thermal instability has precluded any catalytic application so far. By using multiple inorganic cation and charge density mismatch approaches, we