In the present research it is reported the development and characterization of novel polymer blends based on chitosan and poly(vinyl alcohol) (PVA). The hybrid polymeric network was synthesized and modified by chemical crosslinking using genipin for potential use in a variety of biomedical applications. The micro and nanostructures of the blended hydrogels and hybrids were characterized through Fourier Transform Infrared spectroscopy (FTIR) and swelling test analysis. Moreover, cytotoxicity and cell viability were also performed by MTT assay with cell culture. The chemical crosslinking was achieved via the relative intensity of the band at 1650 cm(-1) which is mostly associated with the reaction of genipin carboxymethyl group with the amino group of chitosan forming amides. It was found that by increasing the chitosan content relative to PVA the swelling index of the blend has decreased, reflecting the reduction on the mobility of polymer network and the hydrophilic behavior of the blend. The tested hydrogels have clearly presented adequate cell viability, non-toxicity and suitable properties which can be tailored for potential use in bioengineering applications.