Oligomerization of phenylferrocenylacetylene under the action of WCl6

► Oligomers of phenylpherrocenyl acetylene were synthesized in the presence of WCl6 for the first time. ► Polyenes with pendant ferrocene and benzene moieties were obtained in up to 30% yields. ► The polyenes synthesized are promising macromonomers and building blocks for high-tech materials.