Based on the photocatalytic properties of oxide semiconductors and the ability to degrade organic molecules, the surface-enhanced Raman scattering (SERS) substrates can be reused, a composite structure based on Ag nanoparticles decorated on TiO2 nanorod arrays with graphene (TiO2/graphene/Ag) for surface Raman enhancement is presented. The TiO2 nanorods are synthesized with a hydrothermal method, the TiO2/graphene/Ag composites are fabricated by wet transfer graphene and a photoreduction method. Rhodamine 6G serves as the probe analyte. The results indicate that with the increase of UV irradiation time, the Raman signal of probe molecules weakened, the maximum enhancement factor value is calculated to be about 2.6×106. In addition, the UV self-cleaning properties of TiO2/graphene/Ag composite structure have been studied experimentally, the results indicate that after UV irradiation for 20 min, the Raman intensity dropped to 42.3%, which has a certain UV cleaning effect.