To get high efficiency photodegradation on pollutants under visible light, Pr(III) doped Y2SiO5 upconversion materials and anatase TiO2 nanofilm coated Pr:Y2SiO5 composite have been prepared by using a sol-gel method. XRD and SEM test results indicated that TiO2 nanofilm was well coated on Pr:Y2SiO5 to form TiO2@Pr:Y2SiO5 composite particles with the sizes of 0.5–1.0 μm. To avoid secondary pollution resulting from incomplete recovery of catalyst particles, TiO2@Pr:Y2SiO5 was loaded on the glass fiber filters by using a dip-coating method. It is found that the catalyst particles were embedded into the carrier firmly, even after having been reused for 6 times. The luminescence intensities of TiO2@Pr:Y2SiO5 were getting down sharply with the coating contents of TiO2 increased, which was attributed to the adsorption of the luminescence by the TiO2 film in situ. As a result, TiO2@Pr:Y2SiO5 with 4% TiO2, which presented lowest luminescence intensity, showed the highest efficiency on the photodegradation of nitrobenzene wastewater. The catalysts loaded on glass fiber filters showed excellent reusability on the photodegradation of nitrobenzene and presented a photodegradation rate of 95% at the first time and up to 75.9% even after 6 times of reusing by the treatment time of 12 h.