A new method for the build-up of non-centrosymmetric multilayers has been developed, based on physisorption of polyelectrolytes and subsequent "pole reversal" by chemical activation. The multilayers obtained are characterized by UV-Vis spectrometry, X-ray reflectometry, ellipsometry, time-of-flight secondary ion mass spectroscopy and measurements of the zeta-potential. In the chemical activation step of the multilayer build-up, a non-linear optical chromophore is formed, allowing second harmonic generation experiments which corroborate the non-centrosymmetric structure of the multilayers prepared, as well as demonstrating the non-centrosymmetry arrangement of the chromophores created.