NaH3(SO3)3(CF3)3 crystallizes in the cubic I2_13 space group. The structure consists of twenty-four trifluoromethane molecules inside a NaH3(SO3)3 framework. In the NaH3(SO3)3 framework, Na(1) is bonded in an octahedral geometry to three equivalent O(1) and three equivalent O(3) atoms. All Na(1)-O(1) bond lengths are 2.36 Å. All Na(1)-O(3) bond lengths are 2.33 Å. H(1) is bonded in a single-bond geometry to one O(2) atom. The H(1)-O(2) bond length is 0.94 Å. S(1) is bonded in a distorted trigonal non-coplanar geometry to one O(1), one O(2), and one O(3) atom. The S(1)-O(1) bond length is 1.40 Å. The S(1)-O(2) bond length is 1.52 Å. The S(1)-O(3) bond length is 1.39 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one S(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one H(1) and one S(1) atom. In the third O site, O(3) is bonded in a linear geometry to one Na(1) and one S(1) atom. Linkers: 24 [O]S([O])(O)C(F)(F)F. Metal clusters: 8 [Na]. The MOF has largest included sphere 5.32 A, density 1.48 g/cm3, surface area 3988.26 m2/g, accessible volume 0.28 cm3/g