In the present work, novel hybrid nanostructured composites were produced to be used in many potential applications such as biomedical, drug delivery systems, tri-dimensional scaffolds for biomaterials and tissue engineering, biomembranes and optical devices among others. Hybrids were synthesized by reacting poly (vinyl alcohol) (PVA) in aqueous acid solution with silicon alcoxide tetraethoxysilane (TEOS). PVA/TEOS hybrids were also modified in the nanometer-scale by crosslinking with glutaraldehyde (GA) during the synthesis involving hydrolysis and policondensation of PVA/TEOS. The hybrids were characterized by Fourier Transform Infrared Spectroscopy (FTIR), Small Angle X-ray Scattering (SAXS) and Scanning Electron Microscopy (SEM). FTIR spectra have shown major vibration bands associated with organic-inorganic chemical groups present in the hybrid composite PVA/TEOS. Also, typical absorption bands related to glutaraldehyde alkyl chain have indicated the crosslinking reaction of the hybrid network with glutaraldehyde (PVA/TEOS/GA). SAXS results have indicated different nano-ordered disperse phases for PVA, PVA/TEOS hybrid and PVA/TEOS/GA chemically crosslinked hybrid. SEM micrographs have shown morphology difference between PVA and PVA hybrid samples.