The structural order of native starch granules with different crystalline patterns was analyzed by combined X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) and the results were compared to that of X-ray diffraction (XRD). The FTIR spectra of 13 starch samples were evaluated by principal component analysis (PCA). The main differences among the polymorphs were observed in the intensity of two regions: the OH vibration region, 3650-3000cm(-1), and the region of major adsorption bands, 1200-800cm(-1). The variation in these regions showed that two different groups can be distinguished, one for B-type starches and one for A- and C-type starches. A-type starches exhibited a well-resolved band at 1022cm(-1), suggesting that A-type starch granules have a greater amount of ordered short-range double helices than B-type starches. The intensity and shape of the OH band were different for the three starches and were associated with different local molecular environments of the two water populations of the starch granule. The PCA analysis for X-ray diffraction patterns showed a clear segregation between A- and B-type starches, defined by three typical diffraction peaks at 2=15.0 degrees, 18.1 degrees and 23.1 degrees for A-type starches. There was no correlation in the crystallinity degree obtained by the FTIR and XRD methods.