Layer-by-layer formation for pi-conjugated azomethine multilayers bonded on substrates was investigated. The multilayers were synthesized using ethanol (EtOH) and dichloromethane (DCM) as reaction solvents. The multilayer characteristics were analyzed using UV-vis absorption spectroscopy, ellipsometric thickness, and atomic force microscopy. The absorption spectra and ellipsometric thicknesses of multilayers formed using EtOH and DCM were compared. The results indicate that EtOH is more suitable than DCM for such layer-by-layer formation. In addition, bandgaps estimated from the absorption edge of multilayers were investigated. The results indicate that the bandgap decreases as the number of benzene rings contained in the molecular chain of the multilayer increases. Also, a multilayer with four benzene rings bonded on a substrate had a bandgap close to that of a polymer with a similar chemical structure. (c) 2010 Elsevier B.V. All rights reserved.