From an aqueous solution of (Mo-VI-Mn-IV-CH3COOH), an orange crystal was isolated, which consists of Waugh-type polyoxometalate K-3(NH4)(3)[MnMo9O32]center dot 9H(2)O (I). Its structure is established by single-crystal X-ray diffraction, IR spectroscopy and UV-Vis absorption. Thermogravimetric analysis and cyclic voltammetry measurement were also reported. Compound (I) crystallizes in the Trigonal system, R32 space group with a = 15.747 (8) angstrom, b = 15.747 (6) angstrom, c = 12.377 (6) angstrom, gamma = 120 degrees (8), V = 2657.9 (3) angstrom(3), and Z = 3. We can see in (I), a pair of enantiomers, originated from the homochiral Waugh-type polyoxometalate building units, which are further interact with the potassium ions forming two kinds of alternately arranged 2D polymeric sheets. The whole is linked by hydrogen bonding interactions through ammonium ions and water molecules to form a three-dimensional supramolecular structure. The prevalence of these interactions is illustrated by Hirshfeld surface analyses. Results of cations sensing of Cu2+, Ni2+, Cd2+, Fe2+, Mg2+ and Pb2+ by K-3(NH4)(3)[MnMo9O32]center dot 9H(2)O are also investigated in this work.