NbZn3P4(O8F)2 crystallizes in the orthorhombic Fddd space group. Nb(1) is bonded to four equivalent O(1) and two equivalent F(1) atoms to form NbO4F2 octahedra that share corners with four equivalent P(1)O4 tetrahedra. All Nb(1)-O(1) bond lengths are 1.98 Å. Both Nb(1)-F(1) bond lengths are 1.92 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent O(3) and two equivalent O(4) atoms to form distorted ZnO4 tetrahedra that share corners with four equivalent P(1)O4 tetrahedra. Both Zn(1)-O(3) bond lengths are 1.94 Å. Both Zn(1)-O(4) bond lengths are 1.94 Å. In the second Zn site, Zn(2) is bonded to four equivalent O(2) atoms to form ZnO4 tetrahedra that share corners with four equivalent P(1)O4 tetrahedra. All Zn(2)-O(2) bond lengths are 1.94 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O4F2 octahedra,  a cornercorner with one Zn(2)O4 tetrahedra, and corners with two equivalent Zn(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 39°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.51 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Zn(2) and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Zn(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Zn(1) and one P(1) atom. F(1) is bonded in a single-bond geometry to one Nb(1) atom. Linkers: 32 [O]P([O])([O])=O. Metal clusters: 8 [Nb] ,24 [Zn]. The MOF has largest included sphere 4.41 A, density 2.23 g/cm3, surface area 2550.06 m2/g, accessible volume 0.18 cm3/g