Carbon/silica nanocomposite films with a hexagonal P6mm structure were fabricated directly by the oxidation and carbonization of surfactant/silica nanocomposite films, which were obtained by a dip-coating technique through a combination of sol-gel and evaporation-induced self-assembly. The as-synthesized nanocomposite films were characterized by scanning electron microscopy, X-ray diffraction, transmission electron microscopy and N2 adsorption-desorption. These analyses reveal that the carbon/silica nanocomposite films, with a narrow pore size distribution of mesopores, have an ordered symmetric structure. The pore sizes of this hybrid film can be controlled within a certain range by changing the carbonization temperature. In addition, the films are composed of a continuous silica matrix and a continuous carbon coating in about 1 nm adhered well to the silica matrix. The formation of carbon coatings from surfactant acts as a framework support to prevent the pore size of the silica matrix from shrinking.