A hierarchical structured TiO2@C photocatalyst has been fabricated by using P25 as model nano-photocatalyst and dictyophora indusiata as a natural hierarchical template, which showed significantly higher photocatalytic performance in comparison with P25 and M-TiO2@C. The enhanced catalytic properties can be mainly ascribed to the formation of titanium vacancy and promoted diffusion and transport of substrate molecule benefited from the hierarchical structure.