The physical properties such as the equilibrium water content, the melting enthalpy, the isothermal swelling kinetics and the non-isothermal dehydration kinetics of the composite hydrogels of poly(vinyl alcohol) (PVA) and chitosan (CS) were determined in this work. The influence of the composition and preparation parameters of the hydrogels on these properties was discussed. The results indicate that, PVA/CS composite hydrogel have a proper network structure to support water, and to work as an artificial cartilage material. Combining CS and PVA leads the crystallinity of gel to be weakened, but the interaction between water and gel scaffold to be enhanced. Though the mechanical tensile strength was lowered, but the biocompatibility and the degradation capacity of the gel were optimized. As a class of biomedical functional materials, PVA/CS hydrogel has a great potential application in cartilage scaffold. And as a model system of theoretical research, it promotes the application of thermodynamics in biomedical functional materials.