Alkali treatment can change the structures and properties of cellulosic fibers. The aim of this work was to study the mechanism of structure changes of Tencel fibers treated with different alkali concentration and two treatment methods. Raman spectrum showed that the molecular conformation of Tencel fibers remained unchanged. XRD (X-ray diffraction) indicated that the crystallinty of Tencel fibers in original length increased while that of fibers in relaxation condition remained unchanged. The average crystallite size increased and the orientation index decreased. The quasi-crystallite disassociation and recrystallization in the quasi-crystalline phase during the process of alkali treatment lead to the changes of the crystallinity and the orientation index of Tencel fibers.