Abstract A new monophosphate of trivalent vanadium and zinc Zn 3 V 4 (PO 4 ) 6 was isolated and its structure has been determined from a single crystal X-ray diffraction study. It crystallizes in the space group P 1 with a = 6.349(2) A, b = 7.869(1) A, c = 9.324(2) A, α = 105.32(1)°, β = 108.66(2)°, and γ, = 101.23(2)°. This tridimensional framework consists of bioctahedral V 2 O 10 units of two edge-sharing octahedra, monophosphate groups, distorted ZnO 6 octahedra, and distorted ZnO 5 trigonal bipyramids. In fact, the [V 4 P 6 O 24 ] ∞ framework can be described as a stacking along b of [V 4 P 4 O 24 ] ∞ layers parallel to the (a, c) plane, interconnected through layers of PO 4 tetrahedra. The [V 4 P 4 O 24 ] ∞ layers are themselves built up from two kinds of [V 2 P 2 O 14 ] ∞ ribbons running along a; the latter are obtained by the assemblage of two [VPO 8 ] ∞ single chains sharing the edges of their octahedra in two different ways. The ZnO 5 bipyramids share two edges with two different V 2 O 10 units, whereas the ZnO 6 octahedra share their apices with the VO 6 octahedra, the PO 4 tetrahedra, and the ZnO 5 bipyramids. A remarkable feature of this structure deals with the presence of numerous triply bonded oxygen atoms.