The metathesis polymerization of 1‐ and 2‐ethynylanthracenes (1‐EA and 2‐EA) and 2‐ and 3‐ethynylphenanthrenes (2‐EP and 3‐EP) in the presence of various WCl6‐based catalysts produced widely conjugated soluble polymers with relatively high molecular weights. The highest weight‐average molecular weights of poly(1‐EA) and poly(2‐EA) reached 61,000 and 26,000, respectively, when Ph4Sn was used as cocatalyst, while those of poly(2‐EP) and poly(3‐EP) reached 23,000 and 65,000, respectively, with Ph3Bi as cocatalyst. In contrast, MoCl5‐based catalysts were hardly or not effective for these monomers. A large red‐shifted peak was observed centering at 570 nm (the cutoff at 750 nm) in the absorption spectrum of poly(1‐EA), while the red‐shifted peaks were seen around 500 nm (the cutoffs near 700 nm) in the spectra of other polymers, indicating wide conjugations of the polymer chains. The configurational structures of all the polymers confirmed by DSC and 1H‐NMR were trans structures. However, poly(1‐EA) and poly(3‐EP) appeared to consist partly of cis structures in their main chains. All of the present polymers showed relatively high thermal stability in air compared with poly(phenylacetylene). © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3131–3137, 1998