β-Hairpin formation is one of the fundamental folding actions in biomacromolecules. We present a linear triblock copolymer synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, that is able to mimic on a very basic level hairpin formation by using π-π stacking interactions between phenyl and 2,3,4,5,6-pentafluorophenyl residues.