By synthesizing the novel molybdenum arsenate complexes, we have obtained eight new structures, namely, (4,4'-bipy)[Zn(4,4'-bipy)(2)(H2O)(2)](2)[(ZnO6)((As3O3)-O-III)(2)Mo6O18] center dot 7H(2)O, 1, [Zn(phen)(2)(H2O)](2)[(ZnO6)((As3O3)-O-III)(2)Mo6O18]center dot 4H(2)O, 2, [Zn(2,2'-bipy)(2)(H2O)](2)[(ZnO6)((As3O3)-O-III)(2)Mo6O18]center dot 4H(2)O, 3, [Zn(H4,4'-bipy)(2)(H2O)(4)][(ZnO6)((As3O3)-O-III)(2)Mo6O18]center dot 8H(2)O, 4, (H(2)4,4'-bipy)[Cu-I(4,4'-bipy)](2)[(H2As2Mo6O26)-Mo-V]center dot H2O, 5, (H(2)4,4'-bipy)(3)[(As2Mo6O26)-Mo-V]center dot 4H(2)O, 6, (H(2)4,4'-bipy)(3)[(As2Mo6O26)-Mo-V(H2O)]center dot 4H(2)O, 7, and (H(2)4,4'-bipy)(2.5)(H3O)[(As2Mo6O26)-Mo-V(H2O)]center dot 1.25H(2)O, 8 (4,4'-bipy = 4,4'-bipyridine, 2,2'-bipy = 2,2'-bipyridine, phen = 1,10-phenanthroline). These structures were determined by single-crystal X-ray diffraction analysis and were further characterized by elemental analysis, IR, XPS spectroscopy, and TG analysis. The structure of 1 is constructed from two-dimensional square gridlike sheets linked by the polyanions [(ZnO6)((As3O3)-O-III)(2)Mo6O18](4-) via hydrogen-bonding interactions to form a three-dimensional supramolecular framework with two types of channels. Compounds 2 and 3 display similar bisupported structures. Compound 4 features a three-dimensional supramolecular architecture. Compound 5 possesses a 1D infinite ladderlike ribbon. Compounds 6-8 are discrete structures exhibiting three isomeric forms of [HxAs2Mo6O26]((6-x)-)(.) Furthermore, compound 8 represents a new isomer B'-[As2Mo6O26(H2O)](6-). In addition, the fluorescent properties of compounds 1-3 are reported.