Macromolecular recognition systems are difficult to construct because extremely high recognition ability is required to form a stable host-guest complex toward macromolecules. Herein, we report a novel host-guest recognition motif based on C-propylpyrogallol[4]arene (PgC(3)) and a commercially available polymer, polyethylene glycol (PEG). The results show that PgC(3) can selectively entrap PEG with higher molecular weights to form bilayered host-guest complex structures. Interestingly, this hostguest recognition is strong enough that PgC(3) is able to adsorb PEG from an aqueous solution efficiently.