Three new silver-vanadate hybrids, [Ag(bpy)]₄V₄O₁₂^.H₂O (I), [Ag(dpa)]₄V₄O₁₂^.4H₂O (II) and Ag₄(pzc)₂V₂O₆ (III) (bpy = 4,4'-bipyridyl, dpa = 1,2-bis(4-pyridyl)-ethane, pzc = pyrazine-2-carboxylic acid), were synthesized by hydrothermal methods and characterized using single crystal X-ray diffraction, thermogravimetric analysis, and UV-Vis diffuse reflectance. The structures of I and II are constructed from metal organic {Ag(L)}⁺ chains that are surrounded and linked by {V₄O₁₂}^4- clusters, while the structure of III is comprised of  a {Ag₂(pzc)}_nⁿ⁺ 3D network with {VO₃}_n^n- infinite chains in the channels. These hybrids are stable in air, but decompose upon heating with the removal of the organic ligands at >190 ^oC for I, >120 ^oC for II and >300 ^oC for III. UV-Vis diffuse reflectance measurements show optical band gaps of 2.77 eV for I, 2.95 eV for II, and 2.45 eV for III. Their photocatalytic activities have been evaluated for the decomposition of methylene blue (MB) under both UV light and visible light. III shows high rates for the decomposition of MB under both UV and visible-light irradiation. However, I and II are only active for the decomposition of MB under UV light. The effect of the three different ligands on their atomic and electronic structures and photocatalytic activities are analyzed and discussed.