Three new silver-vanadate hybrid solids, [Ag(bPY)](4)V4O12 center dot 2H(2)O (I), [Ag(dpa)](4)V4O12 center dot 4H(2)O (II), and Ag-4(pzc)(2)V2O6 (III) (bpy = 4,4'-bipyridine, dpa = 1, 2-bis(4-pyridyl)-ethane, pzc = pyrazinecarboxylate), were synthesized by hydrothermal methods and characterized using single crystal X-ray diffraction (1, P2(1)/c, Z = 4, a = 11.375(2) angstrom, b = 14.281(4) angstrom, c = 13.598(3) angstrom, beta = 91.46(1)degrees; II, P2(1/c), Z = 8, a = 13.5748(3) angstrom, b = 15.3372(4) angstrom, c = 14.1854(3) angstrom, beta= 114.1410(9)degrees; III, P (1) over bar, Z = 2, a = 3.580(1) angstrom, b = 11.839(4) angstrom, c = 19.321(7) angstrom, alpha = 89.110(7)degrees, beta = 87.719(9)degrees, gamma = 86.243(8)degrees), thermogravimetric analysis, and UV-vis diffuse reflectance. The structures of I and II are constructed from neutral {Ag4V4O12}(n), layers of clusters that are pillared via the coordination of organic ligands (bpy for I and dpa for II) to the Ag sites in each layer. Conversely, the structure of III is composed of a three-dimensional {Ag-2(pzc)(+)}n, coordination network with channels containing {VO3-}n chains. The lattice water molecules can be removed upon heating to >= 180 degrees C for I (reversibly) and to >= 120 degrees C for II (irreversibly). All three decompose with the removal of organic ligands at higher temperatures of > 200-300 degrees C. Their optical bandgap sizes were measured to be 2.77 eV for 1, 2.95 eV for II, and 2.45 eV for III, which decrease most notably as a result of the band widening for the more extended vanadate structure in III. All three hybrid solids are photocatalytically active for the decomposition of methylene blue under UV light (lambda < 400 nm; 1.01, 0.64, and 2.65 mg L-1 h(-1) for I, II, and III, respectively), while only III exhibits a high activity under visible-light irradiation (lambda >= 400 nm; 1.20 mg L-1 h(-1)). These new hybrid solids are among the first reported to exhibit high photocatalytic activities under either ultraviolet or visible-light irradiation and have also been analyzed with respect to the effect of the different organic ligands on their atomic- and electronic-structures.