The interactions of collagen, with polyphenol and aldehyde, have been investigated using a number of analytical techniques such as DSC and size distribution. The collagen was simulated with hide powder. The stable Matrices can be obtained by polyphenol and aldehyde materials, and high resistance to thermal stability of Matrices can build high thermal stability to collagen. The results also showed that amino groups had more important influence to thermal stability of collagen than that of carboxyl groups. And the size distribution of Matrix formed by poly catechin-oxazolidine is 30 to 50 nm, which can supply high thermal stability for collagen.