The crystalline structure of beta-chitin from squid pen was investigated by X-ray diffraction (XRD). The purified beta-chitin was prepared from bigfin reefsquid pen. beta-Chitin was treated with saturated calcium chloride dihydrate/alchohol (CaCl(2).2H(2)O/MeOH) solvent system at different conditions for XRD studies. The change of crystallinity of beta-chitin from squid pen was studied by using the fiber photographs on imaging plates. The results showed that the diffraction peak (010) was shifted. It means that the lattice plane (010) interplanarilly spreaded to 3.4A, when the squid pen was washed with water after treatment of Ca solvent. Furthermore, when the squid pen was dried after treatment of Ca solvent and washing with water, interplanar spacing of (010) inversely shrank to 1.1A. These results suggested that Ca solvent especially influences the plane (010) of beta-chitin structure.