This work focused on the development of a novel method for molecular level assembly and processing of inorganic-organic hybrid second-order nonlinear optical (SONLO) multilayer films. Aromatic diazo group linked silicon sol was first synthesized and used as a polycation. This oligomer was assembled into inorganic-organic hybrid SONLO multilayer films by electric-field-induced layer-by-layer assembly technique with a low molecular weight chromophore molecule as an anion. After UV irradiation. the electrostatic interaction between layers converted to covalent bonds. Large second-harmonic generation signal of the assembled film was observed, which confirmed that the chromophore in the film had a high degree of molecular orientation as assembled under the electric field. As the cross-linked structure and silicon oxygen meshwork in the films, the resulting inorganic-organic hybrid multilayer films displayed good thermal and chemical stability, and excellent NLO properties. (C) 2009 Elsevier Inc. All rights reserved.