In the present paper the difference in the structure and properties of Lyocell fibers with different hemicelluloses content was investigated. The supermolecular structure and the morphological characterization were compared. The fibril aggregation size was estimated by the cross-polarization magic-angle spinning carbon-13 nuclear magnetic resonance (CP/MAS C-13-NMR) spectroscopy. Meanwhile, the difference in the mechanical, the fibrillation resistance and the dyeing properties of Lyocell fiber with different hemicelluloses content was also analyzed.