A series of B-doped graphene (BG)/rod-shaped TiO₂ (RT) nanocomposites were firstly synthesized via a facile one-step hydrothermal reaction in NaBH₄ aqueous solution. The photocatalytic activity of the obtained nanocomposites for the oxidative photo-destruction of NO_X gas was investigated, and they showed better photocatalytic properties than pure TiO₂ and graphene/TiO₂ nanocomposites. This work could provide new insight into the fabrication of TiO₂–carbon nanocomposites as high performance photocatalysts and facilitates their application in addressing environmental protection issues.