A shape-persistent cryptand 1, containing two face-to-face oriented electron-deficient 2,4,6-triphenyl-1,3,5-triazine units separated by approximately 7 Å, and bridged by two rigid 1,8-naphthyridine linkers and a pentaethylene oxide loop, is created for capturing polycyclic aromatic hydrocarbons. Cryptand 1 formed 1:1 complexes with PAH guest molecules, such as phenanthrene (6), anthracene (7), pyrene (8), triphenylene (9), and tetraphene (10). The single-crystal structure of complex 6⊂1 revealed that 6 was included in the cavity of 1 via face-to-face π···π stacking interactions. Soaking crystalline 1 in a toluene solution of anthracene resulted in anthracene from the toluene solution being picked up by the crystalline solid of 1.