β-Zn3(PO4)2 crystallizes in the monoclinic space group P 21/c with lattice parameters, a = 9.393(3) Å, b = 9.170(6) Å, c = 8.686(3) Å, β = 125.73(10)°, and Z = 4. The three independent cations are strongly ligated to 4, 5, and 5 oxygen atoms, with average Zn—O bond distances of 1.98 ± 0.09 Å, 2.10 ± 0.10 Å, and 2.08 ± 0.13 Å respectively. In addition there are two longer Zn—O distances of 2.51 Å and 2.55 Å in this structure. The PO4 groups exist as independent, nearly regular tetrahedra, with each oxygen atom ligated to two cations. Unlike the structures found for the α and γ phases of Zn3(PO4)2, which contain ribbons and sheets respectively as the basic cation coordination motif, the structure of β-Zn3(PO4)2 contains interconnected sheets.