The invention relates to a catalyzed ozonation film reactor with total removal rate of organic carbon over 99%, which mainly comprises a original water tank, a treatment water tank and an ozone generator, wherein the outlet of the original water tank is connected with an inlet at the lower part of the side of a newly arranged film assembly by a pipeline and a metering pump on the pipeline; the outlet of the ozone generator is connected with an inlet at the top of a buffer tank by a pipeline; an outlet at the top of the buffer tank is communicated with a hollow fiber film inner-cavity through the inlet on the top of the film assembly by a pipeline and a gas flow meter on the pipeline; after a water outlet at the upper part of the side of the film assembly is connected with a pipeline and athree-way pipe on the pipeline to form two pathes, one path is connected with the original water tank, and the other path is connected with the treatment water tank through a flow meter on the original water tank. The ozone generator and a pressure sensor on the top of the buffer tank are respectively connected with a PLC automatic control device by an electric wire. Hollow fiber film threads formed by blending nanometer TiO2 with polyvinylidene fluoride is filled in the film assembly. The ozone becomes liquid phase through the hollow fiber film inner-cavity of the film assembly in the existence of bubble points.