Reaction of t-butylcalix[8]arene (BCA[8]) as an As-type monomer with hexamethylene diisocyanate as a B-2-type monomer was examined to afford only soluble polymers in high yields. Analysis by 1H NMR, IR, MALDI-TOF mass spectroscopy, and AFM indicated that the synthesized polymers consist of nanoscale-gel-shaped structures that contain fixed holes and cavities. We designated this class of polymers as botryosin, after the Greek word botrys, meaning a bunch of grapes. Examination of host guest chemistry of the synthesized polymers revealed complexation with alkali metal ions.