X-Ray diffraction analysis of the a-cyclodextrin complexes with a number of organic guest molecules were carried out. Several different kinds of the X-ray diffraction patterns were obtained. It was found that different guest molecules enclosed within the void of the dextrin cause large changes in the diffraction patterns of the complexes. However, most of the diffraction patterns could be reasonably interpreted in terms of the hexagonal unit cells with minor differences in the unit cell dimensions ranging a=b=27.0~27.8 A and c= 14.7 ~ 16.7 A. The crystal structure of the complexes could be accounted for by a closest packing of channel cylinders that are made by coaxial alignments of the dextrin molecules and the cage structure in the crystal, in which the dextrin molecules align non-coaxially, may not be plausible.