Complexes formed between porphyrins and cyclodextrins are among the most fascinating targets of host-guest complexes. So far, the structural details have been discussed on the basis of the solution properties. However, the real complex structure determined from single-crystal analysis is not known up to the present. In this paper, we report the first successful example for formation of a single crystal and its X-ray analysis. We believe that the resultant dye-oriented crystalline material would lead to novel host-guest chemistry applicable to new photo and electronic devices.