V3P4H8(CO3)4 crystallizes in the orthorhombic Pccn space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a distorted square co-planar geometry to one O(1), one O(2), one O(3), and one O(4) atom. The V(1)-O(1) bond length is 1.95 Å. The V(1)-O(2) bond length is 1.99 Å. The V(1)-O(3) bond length is 1.99 Å. The V(1)-O(4) bond length is 1.96 Å. In the second V site, V(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(5) and two equivalent O(6) atoms. Both V(2)-O(5) bond lengths are 1.96 Å. Both V(2)-O(6) bond lengths are 1.97 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a distorted water-like geometry to one P(1) and two equivalent H(1,2) atoms. The C(1)-P(1) bond length is 1.80 Å. Both C(1)-H(1,2) bond lengths are 0.97 Å. In the second C site, C(2) is bonded in a distorted water-like geometry to one P(2) and two equivalent H(3,4) atoms. The C(2)-P(2) bond length is 1.80 Å. Both C(2)-H(3,4) bond lengths are 0.97 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded in a tetrahedral geometry to one C(1), one O(1), one O(3), and one O(6) atom. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(6) bond length is 1.53 Å. In the second P site, P(2) is bonded in a tetrahedral geometry to one C(2), one O(2), one O(4), and one O(5) atom. The P(2)-O(2) bond length is 1.53 Å. The P(2)-O(4) bond length is 1.52 Å. The P(2)-O(5) bond length is 1.52 Å. There are two inequivalent H sites. In the first H site, H(1,2) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(3,4) is bonded in a single-bond geometry to one C(2) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one V(1) and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. Linkers: 8 [O]P([O])(=O)CCP([O])([O])=O. Metal clusters: 12 [V]. The MOF has largest included sphere 5.40 A, density 1.59 g/cm3, surface area 3063.87 m2/g, accessible volume 0.32 cm3/g