In this study, the free-standing electrospun nanofibrous mat (i.e., nanofelt) consisting of anatase-phase TiO2 nanofibers with diameters of ∼200 nm was prepared, and the nanofelt was subsequently surface-decorated with Ag nanoparticles via an electroless plating method. The sensitivity toward surface enhanced Raman scattering (SERS) and UV-cleanable property of electrospun TiO2/Ag nanofelt were then investigated. In the SERS tests, the target analyte (i.e., 4-mercaptobenzoic acid, Rhodamine 6G, and 4-aminothiophenol) was first adsorbed onto the TiO2/Ag nanofelt as the probe analyte; this was followed by the measurements of Raman intensity and SERS maps. Thereafter, the nanofelt adsorbed with target analyte was cleaned and regenerated/recovered upon UV irradiation in O2-saturated water, and the removal of target analyte was attributed to photodegradation property of anatase-phase TiO2. This study suggested that the electrospun TiO2/Ag nanofelt would be promising as SERS-active substrate with UV-cleanable property for cost-effective and reproducible SERS applications.