Abstract Current progress in the synthesis and properties of conjugated polymers is presented by focusing on recently put forward hyperstructured helical polyacetylene. Interfacial polymerization of acetylene has been carried out in an asymmetric reaction field consisting of chiral nematic liquid crystal (N*‐LC) and Ziegler–Natta catalyst. Since the chiral nematic liquid crystal is composed of nematic liquid crystal and a chiral compound such as axially chiral binaphthyl derivative with R ‐ or S ‐configuration, the screw directions of the polyacetylene chain and fibril bundle and even the spiral morphology are rigorously controlled by selecting the chirality of the chiral compound. Surprisingly, the screw directions of the fibril and the bundle of fibrils in helical polyacetylene were found to be opposite to that of N*‐LC. It is worthwhile to emphasize that the hierarchical spiral morphology involving the primary to higher order structure is generated in a synthetic polymer such as polyacetylene by using N*‐LC as an asymmetric polymerization solvent. Copyright © 2007 Society of Chemical Industry