Two compounds of disphosphopentamolybdate(VI) with the formulae (C4H14N2O)3- [P2Mo5O23] · 3H2O (1) and (C4H14N2O)5(NH4)2[P2Mo5O23]2 · 5H2O (2) have been synthesized by a simple, fast and efficient microwave method, and their crystal structures and spectroscopic properties have been studied. The heteropoly anion [P2Mo5O23]6- has a known structure built of five MoO6 octahedra and two PO4 tetrahedra. The MoO6 octahedra form a pentagonal ring by sharing four edges and one corner and the PO4 tetrahedra are attached to one side of the ring by three oxygen atoms. The most interesting feature of compound 1 is its extensive framework based on a one-dimensional zigzag chain. In compound 2, a more extensive and complicated framework of hydrogen bonds joins the anions, organic cations and water molecules together.