Inorganic-organic hybrid materials were prepared with a cycloaliphatic epoxide adduct of linseed oil with tetraethylorthosilicate (TEOS) oligomers via a cationic LTV-curing process. The TEOS oligomers were prepared in the presence of water and ethanol with hydrochloric acid as a catalyst. The TEOS oligomers were characterized with H-1 and Si-29 NMR and matrix-assisted laser desorption/ionization time-off-light mass spectrometry. Hybrid films were cured, and the dynamic mechanical and thermal properties of the hybrid films were evaluated as a function of the TEOS oligomer content. The morphology of the hybrid films was examined with atomic force microscopy, transmission electron microscopy, and small-angle light scattering. The microscopy and dynamic mechanical data indicated that the hybrid films were heterogeneous materials with various inorganic particle sizes dispersed within the organic matrix. In addition, Si-29 solid-state NMR spectroscopy was used to investigate the coupling between the silicate region and organic regions. A schematic model is proposed to address structural features of hybrid materials. (c) 2005 Wiley Periodicals, Inc.