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A combination of polyanion size and charge allows the Keggin-type polyoxometalate (POM), [CuPW₁₁O₃₉]^5–, a catalyst for some air-based organic oxidations, to fit snuggly in the pores of MOF-199 (HKUST-1), a metal–organic framework (MOF) with the POM countercations residing in alternative pores. This close matching of POM diameter and MOF pore size in this POM–MOF material, [Cu₃(C₉H₃O₆)₂]₄[{(CH₃)₄N}₄CuPW₁₁O₃₉H] (1), results in a substantial synergistic stabilization of both the MOF and the POM. In addition, this heretofore undocumented POM–MOF interaction results in a dramatic increase in the catalytic turnover rate of the POM for air-based oxidations. While 1 catalyzes the rapid chemo- and shape-selective oxidation of thiols to disulfides and, more significantly, the rapid and sustained removal of toxic H₂S via H₂S + 1/2 O₂ → 1/8 S₈ + H₂O (4000 turnovers in <20 h), the POM or the MOF alone is …