Octupolar films containing 1,3,5-tricyano-2,4,6-tris(p-diethylaminostyryl) benzene in a polymethylmetacrylate matrix are prepared by using free-casting and spin-coating methods and their physical properties are characterized by using polarization microscopy, X-ray diffraction spectra, and second-harmonic generation (see figure). The films exhibit an optimum molecular packing that can find useful applications in electro-optic devices.