Chromophoric multilayer thin films exhibiting efficient second harmonic generation have been constructed on inorganic substrates via a stepwise layer-by-layer process using molecular self-assembly techniques. In each step, chemical species bearing appropriate functional groups form covalent bonds with functional groups deposited in the previous step. Bulk acentricity is achieved by the orientation of chromophore-containing layers outward from the substrate surface. A new chromophore having comparable hyperpolarizability but different steric and transparency characteristics than the stilbazolium chromophore used previously has been incorporated into self-assembled films. The large effects of octachlorotrisiloxane capping on the structure of these films have been investigated by second harmonic generation and X-ray reflectivity measurements. Novel in situ measurements of second harmonic generation efficiency as a function of chromophore layer growth are described and provide information useful for optimizing deposition conditions and understanding the film growth process.