V5P4H4(CO8)2 crystallizes in the orthorhombic Pmmn space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one V(1), one O(4), two equivalent O(1), and two equivalent O(2) atoms. The V(1)-V(1) bond length is 0.60 Å. The V(1)-O(4) bond length is 1.65 Å. There is one shorter (1.97 Å) and one longer (2.04 Å) V(1)-O(1) bond length. There is one shorter (2.00 Å) and one longer (2.05 Å) V(1)-O(2) bond length. In the second V site, V(2) is bonded in a rectangular see-saw-like geometry to four equivalent O(3) atoms. All V(2)-O(3) bond lengths are 1.97 Å. C(1) is bonded in a distorted tetrahedral geometry to two equivalent P(1) and two equivalent H(1,2) atoms. Both C(1)-P(1) bond lengths are 1.80 Å. Both C(1)-H(1,2) bond lengths are 0.97 Å. P(1) is bonded to one C(1), one O(1), one O(2), and one O(3) atom to form corner-sharing PCO3 tetrahedra. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.52 Å. The P(1)-O(3) bond length is 1.53 Å. H(1,2) is bonded in a single-bond geometry to one C(1) atom. There are four inequivalent O sites. In the first O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(1) atom. In the second O site, O(4) is bonded in a single-bond geometry to one V(1) atom. In the third O site, O(1) is bonded in a 3-coordinate geometry to two equivalent V(1) and one P(1) atom. In the fourth O site, O(2) is bonded in a distorted single-bond geometry to two equivalent V(1) and one P(1) atom. Linkers: 4 [O]P([O])(=O)CP([O])([O])=O. Metal clusters: 10 [V]. The MOF has largest included sphere 5.43 A, density 2.15 g/cm3, surface area 2341.56 m2/g, accessible volume 0.20 cm3/g