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As a new textile fiber produced from Neosinocalamus affinis, the structures of the bamboo fiber were studied thoroughly in this research. Using Fourier-transform infrared (FTIR) (using a Micro-FTIR Spectrometer), X-ray diffraction (XRD), nuclear magnetic resonance (NMR) spectroscopy and scanning electron microscopy (SEM), we investigate the chemical composition, crystalline structure, molecular and morphology structure, respectively. Results show that the chemical composition of bamboo fiber is the same as all bast fibers, that is, cellulose constitutes the majority and lignin needs to be reduced further for textile applications. The bamboo fiber belongs to cellulose I crystalline structure as flax, cotton and ramie, while has a small molecular mass and a low degree of polymerization. The cross section of the single bamboo fiber is round with small lumen. It can be predicted that bamboo fiber has high breaking strength, but low elongation and has good water absorption properties. The structural characteristics of the bamboo fiber are different from those of other textile plant fibers.