This paper describes the development of a new crosslinking method for the synthesis of novel hydrogel films from chitosan and PVA for potential use in various biomedical applications. These hydrogel membranes were synthesized by blending different ratios of chitosan (CS) and poly(vinyl alcohol) (PVA) solutions and were crosslinked with 2.5% (w/v) triethyl orthoformate (TEOF) in the presence of 17% (w/v) sulfuric acid. The physical/chemical interactions and the presence of specific functional groups in the synthesized materials were evaluated by Fourier transform infrared (FT-IR) spectroscopy. The morphology, structure and pore size of the materials were investigated by scanning electron microscopy (SEM). Thermal gravimetric analysis (TGA) proved that these crosslinked hydrogel films have good thermal stability which was decreased as the CS ratio was increased. Differential scanning calorimetry (DSC) exhibited that CS and PVA were present in the amorphous form. The solution absorption properties were performed in phosphate buffer saline (PBS) solution of pH 7.4. The 20% PVA-80% CS crosslinked hydrogel films showed a greater degree of solution absorption (183%) as compared to other compositions. The hydrogels with greater CS concentration (60% and 80%) demonstrated relatively more porous structure, better cell viability and proliferation and also revealed good blood clotting ability even after crosslinking. Based on the observed facts these hydrogels can be tailored for their potential utilization in wound healing and skin tissue engineering applications. © 2015 Elsevier B.V. All rights reserved.