A poly(phenylacetylene) bearing a polycarbohydrate ionophore as a graft chain (copolymer 4) was synthesized by the copolymerization of end‐functionalized (1→6)‐2,5‐anhydro‐3,4‐di‐O‐ethyl‐D‐glucitol with a 4‐ethynylbenzoyl group (macromonomer 2) with phenylacetylene. Copolymer 4 showed a split‐type circular dichroism (CD) in the long absorption region of the conjugated polymer backbone (280–500 nm), and the CD pattern varied in response to external stimuli, such as the solvents and temperature. This suggested that 4 had a predominantly one‐handed helical conformation in the polyacetylene backbone. The CD pattern of 4 was completely inverted by the formation of a complex between the macromolecular ionophore units and the selected metal cations, that is, Ba2+, Pb2+, Sr2+, Na+, and Li+. This suggested that copolymer 4 underwent a helix–helix transition through the host–guest complexation with achiral inorganic metal cations. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5855–5863, 2005