This invention is concerned with a new method for producing different types of cross-linked hyaluronic acidnullprotein bio-composites. In the process of manufacture, polysaccharide and protein solution are mixed under moderate pH values and salts, and the well mixed solution can be prepared to various types, such as membrane, sponge, fiber, tube or micro-granular and so on. After then, with the bio-compatibility, biodegradation, prolong enzymatic degradation and good physical of bio-composite is formed in the little acid of organic solution that with the cross-linked reagent.