A one-handed helical polymer, syndiotactic poly(methyl methacrylate) (st-PMMA), recognizes the size and chirality of higher fullerenes through an induced-fit mechanism and can selectively extract enantiomers of the higher fullerenes, such as C-76, C-80, C-84, C-86, C-88, C-90, C-92, C-94, and C-96. This discovery will generate a practical and valuable method for selectively extracting the elusive higher fullerenes and their enantiomers and opens the way to developing novel carbon cage materials with optical activities.