The purpose of this study is to develop novel poly(vinyl alcohol) (PVA)/poly(ethylene glycol) (PEG) hydrogel blends and PVA-derived organic-inorganic hybrid materials and perform nanostructural characterizations. PVA and PEG hydrogels were prepared by dissolving the polymer in aqueous solution, followed by addition of glutaraldehyde (GA) chemical crosslinker. Hybrids were synthesized by reacting PVA in aqueous solution with tetraethoxysilane (TEOS). PVA/TEOS were also modified in the nanometer-scale by crosslinking with GA during the synthesis reaction. Hydrogels and hybrids were characterized by using small-angle X-ray scattering synchrotron radiation (SAXS) and Fourier transform infrared spectroscopy (FTIR). Thin film samples were prepared for SAXS experiments. SAXS results have indicated different nano-ordered disperse phases for hydrogels made of PVA, PEG, PVA/GA, PVA/PEG. Also, PVA/TEOS and PVA/TEOS/GA hybrids have indicated different X-ray scattering patterns. FTIR spectra have showed major vibration bands associated with organic-inorganic chemical groups present in the hybrid nanocomposites PVA/TEOS and PVA/TEOS/GA. PVA/PEG hydrogels and PVA-derived hybrid materials were successfully produced with GA crosslinking in nanometer-scale network. (C) 2004 Elsevier Ltd. All rights reserved.