The incorporation of Co(OAc)₂ into ascorbic acid-coated TiO₂ nanoparticles easily provided a new heterogeneous visible-light active titania-based photocatalyst (TiO₂/AA/Co) which was characterized by different techniques such as FT-IR, XPS, ICP-AES, TGA and TEM. A red-shift of the band-edge and a significant reduction of the band-gap (2.8 eV) were demonstrated by UV-DRS. The as-prepared TiO₂/AA/Co nanoparticles possess excellent photocatalytic properties under visible light for the aerobic benzylic C–H oxidation of a structurally diverse set of benzylic alcohols and benzylic hydrocarbons in ethyl acetate as a safe solvent. The spectral results and leaching experiments revealed that the structural integrity of the solid catalyst is well preserved after being reused many times.