Partially deacetylated chitins with different degrees of deacetylation (DD) were prepared by alkaline treatment under homogeneous conditions, and the effect of DD on their solubility was discussed in terms of crystal structure and mode of hydrogen bonding. With an increase in the treatment time, the DD of chitin increased proportionally. The chitin became soluble in dilute acetic acid at the DD of ca. 28% or over and soluble in water at the DD of ca. 49%. The solubility of the partially deacetylated chitins had a close relationship with their crystal structure, crystallinity, and crystal imperfection as well as the glucosamine content. The wide-angle X-ray diffractometry (WAXD) revealed that the chitin with ca. 28% DD retained the crystal structure of alpha-chitin with significantly reduced crystallinity and perfection of the crystallites. The water-soluble chitin of ca. 49% DD had a new crystal structure similar to that of beta-chitin rather than either alpha-chitin or chitosan, suggesting that the homogeneous deacetylation transformed the crystal structure of chitin from the alpha to the beta form. Some hydrogen bonds existing in raw alpha-chitin were found to be missing at a DD of ca. 49%.