The invention discloses a heterogeneous ultraviolet-Fenton oxidation catalyst and preparation and application thereof. Prussian blue is used as iron sources, the Prussian blue is deposited on an amino-functional SiO2 mesoporous film with vertical hole passages in an automatic assembly manner, the Prussian blue is fixed through the physical absorption and the interaction force between the positive and negative charges, the bonding is firm, and the loosing is avoided; the prepared catalyst is the film catalyst, the specific surface area is large, the utilization efficiency of active components is high, the catalytic efficiency is high, and compared with the powdery and granular catalysts, the separation and the recovery are easy. Because the catalyst is provided with the mesoporous passages which are vertically distributed, the internal diffusion resistance is little, and many organic matters are suitable for being treated; at the same time, the Prussian blue loaded by the catalyst contains various states of iron, so that the Prussian blue has a cooperating function; in addition, the preparation method disclosed by the invention is simple in technology and wild in condition, so that the preparation method is suitable for popularization and application.