Collagen materials were crosslinked by 1-ethyl-3-(3-dimethyl aminopropyl) carbodiimide (EDC) in the presence of chondroitin sulfate (CS), one of glycosaminoglycans (GAGs). PVA and chitosan were also blended with collagen. The physical and chemical properties of the matrices were characterized by SEM, DSC, and ESCA, L929 cells were implanted on the matrices to show the cytotoxic and the biological characters of the materials, The results indicate that EDC is an effective and non-cytotoxic cross-link reagent, which can replace the common dialdehyde reagent. The attachment of CS can improve the stability of collagen and accelerate cell growth The addition of PVA can prepare porous matrices with smaller bore size. There are reactions between the chitosan and collagen, and the composite has good biological character, The presence of chitosan can also increase the amount of incorporated CS.