Titanium dioxide/N-doped carbon core/shell nanoparticles enabling efficient visible-light-driven photocatalytic degradation of rhodamine B, considered a model compound for water-soluble environmental pollutants, were successfully prepared by the carbonization of dopamine-grafted TiO2 nanoparticles. These precursor nanoparticles were prepared via simple ligand-to-metal charge transfer (LMCT) between TiO2 nanoparticles and dopamine. Owing to the incorporation of Ti-O-C chelating bonds and the subsequent narrowing of the optical band gap, the dopamine-derivatized photocatalyst demonstrated enhanced activity compared with that of commercial photocatalysts and promoted the photocatalytic degradation of rhodamine B under both UV light and visible light. This LMCT-mediated incorporation of thin amorphous N-doped carbon shells onto the surface of semiconducting photocatalysts may be widely applicable for the generation of novel and robust hybrid materials with enhanced photocatalytic activities for many applications.