Five Well-Dawson-type arsenomolybdates, formulated as [Cu(2,2'-bpy)(2)][{Cu(2,2'-bpy)}(3){As-2(V)Mo-2(V)Mo-16(VI)O-62}] 4H2O (1), [H-2(4,4'-bpy)](2).(5)[As(III)(As-2(V)Mo-2(V)Mo-16(VI)O-62)] 5H(2)O (2), (pyr)(imi)(Himi)(3)[As-2(III)(As-2(V)Mo-3(V)Mo-15(VI)O-62)] 3H(2)O (3), [As-3(III)(As-2(V)Mo-3(V)Mo-15(VI)O(6)2())] 4H(2)O (4), and (H(2)btp)(3)[As-2(V)Mo-18(VI)O-62] 6H2O (5) (bpy = bipyridine, pyr = pyrazine, imi = imidazole, btp = 1,5-bis(triazol)pentane), have been hydrothermally synthesized and structurally characterized by the elemental analysis, TG, IR, UV-vis-NIR, XPS, XRD, and single-crystal X-ray diffraction. The structural analysis indicates that compounds 1-4 contain rare reduced Dawson {As2Mo18O62} (abbreviated as {As2Mo18}) anions as parent cluster unit, which are capped by a certain number of Cu(II) or As(III) species on different coordination positions via altering pH values and organic ligand of the reaction system. Compounds 1 and 2 are asymmetric tricopper and monoarsenate(III) capped assemble by three {Cu(bpy)}(2+) and a {AsO3} fragments, respectively. Compounds 3 and 4 are symmetric biarsenate(III) and triarsenate(III) capped cluster by four and six half occupancy {AsO3} units, respectively. Compound 5 is uncapped {As2Mo18} structures. Compounds 1-4 represent infrequent Dawson arsenomolybdate capped architectures, especially 2-4, as arsenate(III) capped Dawson-type assemblies are observed for the first time. Compounds 1-5 display good electrocatalytic activity on reduction of nitrite. Compounds 1, 2, 3, and 5 exhibit fluorescent properties in the solid state at room temperature. In addition, magnetic properties of 1-4 have been investigated in detail.