Assembly of noncentrosymmetric multilayers is a facile technique for preparing noncentrosymmetric films avoiding electrical poling procedures and problems from subsequent relaxation of the induced orientational order. A maximum chi(zzz) of 13 x 10(-9) esu was achieved for the assembly of up to six layers. Current problems are the long-term hydrolysation of the hemicyanine nonlinear optical chromophores and the reduction of polar orientation with increasing layer thickness.