Mesoporous films with cubic and hexagonal (MCM-48, 41, respectively) symmetries were synthesized at the oil-water interface. The silica precursors were segregated between oil and water phases. The film's formation was studied with small angle X-ray scattering, Brewster angle microscopy, light microscopy techniques and atomic force microscopy. A phase map depicting the aging and heating times required for the cubic phase formation was constructed. Differences in roughness between the silica-oil and silica-water interfaces were analyzed with AFM. It is speculated that the differences are indicative of the mechanism of film formation and growth.