V2O5 powders modified with different theoretical silver contents (1, 5, 10, 15, and 20 wt% as Ag2O) were obtained with acicular morphologies observed by scanning electron microscopy (SEM). Shcherbinaite crystalline phase is transformed into the Ag0.33V2O5 crystalline one with the incorporation and increase in silver content as was suggested by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis. With further increase in silver contents the Ag2O phase appears. Catalysts were active in photocatalytic degradation of malachite green dye under simulated solar light, which is one of the most remarkable facts of this work. It was found that V2O5-20Ag was the most active catalytic formulation and its activity was attributed to the mixture of coupled semiconductors that promotes the slight decrease in the rate of the electron-hole pair recombination.