Reversible addition fragmentation chain transfer polymerization afforded triple hydrogen-bonding block copolymers (PBA-b-PDAD) with well-controlled molecular weight and molecular weight distributions (1.2-1.4). The complexation via specific hydrogen bonding between these block copolymers in CHCl3 provided an unprecedented approach for the formation of spherical vesicles. Atomic force microscopy and dynamic light-scattering measurements revealed that the resultant polymeric vesicles were about 100 nm in radius. Triple hydrogen-bonding interactions between maleimide and PBA-b-PDAD resulted in the dissociation of these spherical vesicles, facilitating the guest molecule recognition. The hydrogen-bonding interaction between maleimide and the PBA-b-PDAD was further confirmed by H-1 NMR and FTIR spectra. These results indicated that these vesicles of triple hydrogen-bonding block copolymer could be a potential new vehicle for molecular recognition. (C) 2016 Wiley Periodicals, Inc.