Abstract TiO 2 is a promising photocatalytic material for hydrogen generation. However, the fast recombination of electron–holes restricts the photocatalytic performance of TiO 2 . Herein, this study demonstrates a 2D‐layered carbon/TiO 2 (C/TiO 2 ) architecture via CO 2 oxidation of 2D‐Ti 3 C 2 , in which the 2D carbon layers provide electron transport channels and improve the hole–electron separation efficiency. Compared to Ti 3 C 2 support, the thickness of derived carbon supports is significantly reduced, which enhances the light intensity arriving at the surface of TiO 2 . The oxidation parameters are investigated systematically. It is found that high temperature and high CO 2 gas flux lead to the formation of crystal TiO 2 and the oxidation of carbon layers. The bandgap of 2D‐layered C/TiO 2 samples is ranged from 2.83 to 2.89 eV. The 2D‐layered C/TiO 2 delivers enhanced photocatalytic activity compared with pure TiO 2 catalysts. The optimal photocatalytic hydrogen evolution rate of 2D‐layered C/TiO 2 is up to 24.04 µmol h −1 , which is about 89 times higher than that of pure TiO 2 . This research broadens the applications of C/TiO 2 hybrids and provides new approach to synthesize novel 2D‐layered materials for photocatalytic applications.