Visible-light-driven Ag3VO4 photocatalysts were successfully synthesized using low-temperature hydrothermal synthesis method. Under various hydrothermal conditions, the structures of silver vanadates were tuned by manipulating the hydrothermal time and the ratio of silver to vanadium. X-ray diffraction (XRD) results reveal that the powders prepared in a stoichiometric ratio consisted of pure α-Ag3VO4 or mixed phases of Ag4V2O7 and α-Ag3VO4. With increasing the Ag-to-V mole ratio to 6:1, the resulting samples were identified as pure monoclinic structure α-Ag3VO4. UV-vis spectroscopy indicated that silver vanadate particles had strong visible light absorption with associated band gaps in the range of 2.2-2.5 eV. The sample synthesized in the excess silver exhibited higher photocatalytic activity than that synthesized in a stoichiometric ratio. The powder synthesized at silver-rich at 140℃ for 4 h (SHT4) exhibited the highest photocatalytic activity among all samples. The reactivity of SHT4 (surface area, 3.52 m2 g-1) on the decomposition of gaseous benzene was about 16 times higher than that of P25 (surface area, 49.04 m2 g-1) under visible light irradiation. A well developed crystallinity of Ag3VO4 of SHT 4 was considered to enhance the photocatalytic efficiency.