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In the literature,it has been found that PCL has the epitaxial relationship with PE substrate leading to parallel alignment of PCL chain with PE chain.The crystallization behavior of the Poly(ε-caprolactone)/Poly(vinyl chloride)blends,a well studied compatible complex,induced by highly oriented polyethylene has been investigated by PLM and FTIR.It has been found that the highly oriented polyethylene can also induce epitaxial crystallization of the blends film when the PCL content is higher than 50 wt%.The newly cast PCL/PVC(50:50)blends film is amorphous and a weak orientation of the blends can be detected induced by the over-layered PE film in the solvent evaporation process.Moreover,the orientation degree can increase continuously when the over-layered PE film has been removed.By comparing the blends film with and without the over-layered PE substrate in the subsequent crystallization process,it can be found that the cold crystallization temperature can influence the orientation degree of the blends greatly.When the crystallization temperature is lower,the blends film with the PE substrate present higher orientation degree than the one that the PE film has been removed.At higher crystallization temperature,the reverse trend can be detected,i.e.,the blends film which has been removed the PE layer has higher orientation degree than the one with PE in the whole crystallization process.The results indicate that the epitaxial crystallization can develop along the vertical direction from the initially induced oriented PCL layer on the surface.PLM result also proved the increase of the orientation degree even after the PE film was removed from the blends.AFM confirmed the inconsistent orientation structure of polymer blends on PE substrate.