Abstract: In order to study the changes of the crystal structure of potato starch, we prepared acid hydrolyzed starch, B-type crystallite starch and V-type compounds of potato starch. The Raman spectroscopy was used to analyze the structure of those starch. By comparing different crystalline structure of Raman spectrum, it can be seen that the peak intensity gradually reduced. The relative peak area is also changed. The formation of complex makes the double helix conversion into the single helix structure. The position of characteristic peaks in different compound were almost the same, but the intensity of peaks showed a big difference.