Studies have been focused on Langmuir films of a family of iridium polyalkoxystilbazole metallo-organic complexes. We report that these polyalkoxystilbazole complexes form stable Langmuir monolayers on water as subphase, and are successfully transferred onto glass substrates for structural and optical characterisations using UV-vis spectroscopy. The area per molecule obtained for the polyalkoxystilbazole films is larger than that for the corresponding monoalkoxystilbazole films, and cannot simply be explained by the cross-sectional area of the Ir(CO2)Cl headgroup, which is common to all of them. The length of the alkoxy chains as well as their position of substitution have an influence on the orientation of the molecules. (c) 2004 Elsevier B.V. All rights reserved.