The invention provides a sunlight full-spectrum responding Ag2O/TiO2/V2O5 nano hetero-structure photocatalyst and a preparation method thereof. The preparation method is characterized by comprising the following steps: mixing tetrabutyl titanate, polyvinylpyrrolidone, absolute ethanol, dimethyl acetamide and glacial acetic acid so as to obtain a solution A, mixing vanadium(IV) oxide acetylacetonate, polyvinylpyrrolidone and dimethyl acetamide so as to obtain a solution B, mixing the solution A and the solution B so as to obtain a polyvinylpyrrolidone/titanate/vanadium(IV) oxide acetylacetonate mixed solution, spinning the mixed solution by an electro-spinning method so as to obtain TiO2/V2O5 nano fibers, then soaking AgNO3 and the TiO2/V2O5 nano fibers in deionized water, injecting a NaOH solution into the deionized water, and drying so as to obtain the Ag2O/TiO2/V2O5 nano hetero-structure photocatalyst. The Ag2O/TiO2/V2O5 nano hetero-structure photocatalyst can well absorb lights in the ultraviolet zone, visible zone, and near infrared zone; at the same time, energy bands of the Ag2O, TiO2, and V2O5 are reasonably matched, thus the photo-produced electronic cavities can be effectively separated, so the Ag2O/TiO2/V2O5 nano hetero-structure photocatalyst has a very high sunlight catalytic activity.