Highly organized and textured CTAB templated silica films are made by the spin-coating technique. The HRTEM structural characterization of these films clearly shows the formation of a 3D hexagonal structure (P63/mmc space group) due to the stabilization of a new phase which does not belong to the phase diagram of CTAB in water. This probably results from the formation in dynamic conditions of a 3D-hexagonal packing of spherical micelles separated by polymeric silica walls. The shrinkage of spin-coated films during the drying leads to values of the c/a hexagonal ratio weaker than the one corresponding to the close packed hexagonal structure. This 3D organization is maintained after removal of the surfactant molecules by calcination, leading to a new mesoporous material.