The structure characteristics, crystalline characteristics and relative crystallinity of starches from flue-cured tobacco leaves were investigated with CP/MAS 13C NMR, X?ray powder diffraction (XRD) and scanning electron microscopy (SEC). The results indicated that there were typical doublets at about 99.3, 100.2 ppm in C1 spectrum of CP/MAS 13C NMR from tobacco starch. The XRD spectra of tobacco starch showed the strongest diffraction peak at around 17 o 2θ, and a few small peaks at around 5.6o, 15o, 20o, 22o and 24o 2θ, which was the characteristic peaks of B?type starch. The percentage of the relative crystallinity and double helix content calculated from CP/MAS 13C NMR in tobacco starches were 36.1% and 21.3%, respectively. The relative crystallinity obtained from CP/MAS 13C NMR was higher than that from XRD.