Ordered dichloro-biphenylene-bridged silsesquioxanes are fabricated by interfacial polymerization at the aqueous/organic phase interface, which involves hydrogen bonding and aromatic pi-pi stacking interaction, which are responsible for the preferential orientation of the organic bridged units. The high-resolution transmission electronic microscopy images and wide angle X-ray powder diffraction patterns reveal the well-ordered features with lamellar spacings in the hybrid silsesquioxanes. Fluorescence spectra and molecular simulation verify the possibility of ordered structure formation. A general model is developed for the formation of ordered 3,3'-dichloro-biphenylene-bridged silsesquioxanes by interfacial polymerization. This method should offer a convenient avenue for the preparation of highly ordered hybrid network materials. (C) 2011 Elsevier Ltd. All rights reserved.