The nanopowders of V2O5 and Mn-doped V2O5 were prepared by the sol–gel processing and characterized by X-ray diffraction. The photoactivity of the prepared catalyst V2O5 and Mn-doped V2O5 under UV irradiation were evaluated by degradation of methyl orange solution. The effect of pH of precursor for V2O5 and doping amount of Mn ions on photocatalytic activity were investigated. The pH value had affected the species of precursor and the crystal morphology. The minimum particle size could approach to 26.5 nm. The result showed the degradation rate of methyl orange could approach 62% at pH=6. While doped with Mn ions, Mn dopant can improve the photocatalytic activity of V2O5 powder. The appearance of the second phase Mn(VO3)2 is also beneficial to increase photocatalytic activity.