Incorporating dopants into the TiO2 single crystals lattice is a big challenge because single crystal has a high crystallinity and the nucleation and growth of TiO2 single crystals is readily subjected to the interference of the dose of dopant precursors. Here, we propose an in situ synthetic strategy for the construct of carbon-doped TiO2 single crystal nanorods using CPS/TiO2 as the precursors of TiO2 nanorods and carbon source via a facile hydrothermal route. This technique involves the preparation of cationic polystyrene spheres (CPS), sequential deposition of TiO2 precursor, hydrothermal reaction, and the pyrolysis of CPS in a N2 atmosphere at 450 °C. The morphology and structure of as-prepared C-TiO2 single crystal nanorods were characterized by TEM, SEM, STEM Mapping, XRD, UV–vis spectroscopy, and XPS. All results confirm the carbon doping in the as-prepared TiO2 single crystal nanorods. As a result of unique microstructure, the resulting TiO2 exhibits remarkably visible-light photocatalytic efficiency for the degradation of organic pollutants including methylene blue (MB), Rhodamine B (RhB) and p-nitrophenol (PNP). Therefore, the current study provides a new insight for incorporating dopants into the TiO2 single crystals lattice.