Hybrid polymer network (HPN) of chitosan (CS) with poly(vinyl alcohol) (PVA) was prepared by using radiation degraded chitosan. The chemical structure of chitosan promoted chain scission reactions upon irradiation which lowered its molecular weight and also changed its hydrophilic balance. The effect of molecular weight and hydrophilicity of irradiated chitosan on structural, thermal and surface properties of the HPN were studied. The increased hydrophilicity of irradiated chitosan lowered the crystallinity of the HPN. The endothermic peak was shifted towards higher temperatures in HPN having irradiated chitosan. The decreased value of contact angle with increasing dose, further confirmed the increased hydrophilicity of the HPN. The cytotoxicity results of HPN showed the viability of human fibroblast cells and their non-toxic nature making it suitable for tissue engineering and other biomedical applications. © 2013 Elsevier Ltd.