The improvement of the photocatalytic performance of TiO 2 nanofibers (NFs), prepared by electrospinning, is achieved by surface modification with the rhodizonic acid (RhA). The condensation reaction between hydroxyl groups from TiO 2 NFs and RhA is accompanied by the red-shift of optical absorption due to interfacial charge transfer (ICT) complex formation. Crystal structure, morphology, and optical properties of unmodified and surface-modified TiO 2 NFs were analyzed. The photocatalytic performance of prepared samples has been examined through degradation of organic dye methylene blue. Superior photocatalytic activity of surface-modified TiO 2 NFs with RhA is attributed to their enhanced optical properties, i.e., the ability to harvest the photon energy in the visible spectral range.