The core–shell nanospheres fullerenol–TiO₂ and C₆₀@2β-CD–TiO₂ were fabricated by a layer-by-layer self-assembly procedure seeding with fullerenols and C₆₀@2β-CD respectively, the nanospheres ranging in size from 40 to 80 nm and 10–20 nm in diameter respectively. The presence of fullerenols in the nanostructures was confirmed by XPS and FT-IR spectroscopy, and the XRD patterns prove both the titania shells on fullerenol and C₆₀@2β-CD are rutile and anatase phases.