In this article, a new methodological approach to the fabrication of organized molecular films with chromophores lying flat on the film surface has been investigated with the design of an azacrown-type multication, 1,4,10-[3-(4-(4'-methoxy-phenylazo)-2-nitro-phenoxy)propyl]-1,4,7,10,13, 16-hexamethylhexaazacyclooctadecane, and LBL film deposition by using the electrostatic self-assembly method. The chromophore alignment was analyzed on the basis of the polarized UV-visible spectra: the tilt angle of the transition moment of trans-azobenzene with respect to the surface normal was determined to 64 +/- 2 degrees, indicating a strong trend for chromophores in the multilayered films to planar alignment.