Hybrid silica xerogels favourably combine the properties of organic and inorganic components in one material; consequently these materials are useful for multiple applications. The versatility and mild synthetic conditions provided by the sol-gel process are ideal for the synthesis of hybrid materials. The specific aims of this study were to synthesise hybrid xerogels in acidic media using tetraethoxysilane (TEOS) and ethyltriethoxysilane (ETEOS) as silica precursors, and to assess the role of the ethyl group as a matrix modifier and inducer of ordered domains in xerogels. All xerogels were synthesised at pH 4.5, at 60 degrees C, with 1:4.75:5.5 TEOS:EtOH:H2O molar ratio. Gelation time exponentially increased with the ETEOS molar ratio. Incorporation of the ethyl groups into the structure of xerogels reduced cross-linking, increased the average siloxane bond length, and promoted the formation of ordered domains. As a result, a transition from Q(n) to T-n signals detected in the Si-29 NMR spectra, the Si-O structural band in the FTIR spectra shifted to lower wavelength, and a new peak in the XRD pattern at 2 theta < 10 degrees appeared in the XRD patterns. Mass spectroscopy detected fragments with high numbers of silicon atoms and a polymeric distribution. (c) 2013 Elsevier B.V. All rights reserved.