Cyclodextrins (CDs) have been found to form pseudo-polyrotaxanes (CDs superset of pFPEs) with poly(hexafluoropropyl ether) s (pFPEs) by mixing bulk pFPEs with aqueous solutions of CDs. The mixture of gamma CD with alpha,omega-diol-pFPE (pFPE-H) gave gamma CDs superset of pFPE-H in 86% yield, which was higher than those of beta CD (47%) or alpha CD (2.4%). In contrast, the mixture of gamma CD with alpha,omega-dicarboxylic acid-pFPE (pFPE-C) gave gamma CDs superset of pFPE-C in a moderate yield (66% yield), but higher threading ratio (80%). The threading ratio of CDs superset of pFPEs depends on the hydrophilicity of the functional end group of pFPEs. The hydrophilic and hydrophobic balance of pFPEs plays an important role to form CDs superset of pFPEs.