We have succeeded in the fabrication of distorted cubic R-3m mesoporous silica film with 3D open mesostructure providing high pore accessibility from the surface-air interface of the film. The film fabrication involves a unique approach of adding 1,3,5-triisopropylbenzene (TIPB) to the silica/cetyltrimethylammoniumbromide (CTAB) coating sol during its preparation. The addition of TIPB induces the formation of spheroid micelles, promoting R-3m mesostructure in the film. This phase does not exist in the corresponding binary phase diagram of CTAB surfactant.