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 (P6(3)/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 cia 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.