Well-defined supramolecular helical nanofibers have been constructed by a rationally designed achiral monomer in aqueous solution based on the 1:2 host–guest combination between cucurbit[8]uril and a 4,4′-bipyridin-1-ium chloride (BPY+) salt derivative. The formed nanostructures could be adjusted by varying the concentration of monomer from helical nanofibers to a pH-responsive hydrogel.