It has recently been demonstrated that hexagonal mesoporous silica films can be grown at mica/water interfaces. In this report it is established that the films can also be synthesized on cleaved pyrolytic graphite. Diffraction and microscopy studies of the growth, structure and form of the films indicate that the channels are aligned along the hexagonal symmetry axes of the graphite surface. The registry of the mesoporous silica film with the underlying substrate may be facilitated by an organized hemicylindrical surfactant monolayer assembly that is observed at the boundary between the graphite and water. Growth of the mesoporous silica film most likely begins within a liquid-crystal surfactant/silicate film that is aligned with the hemimicelle–graphite overstructure.