This work deals with the synthesis and characterization of novel eugenol-based polymers. The polymerization of 2-methoxy-4-propenyl-1-prop-2-ynyloxybenzene (1) with Rh, Mo, and W catalysts gave the corresponding polyacetylene [poly(1)], while that using BF3 catalyst gave poly(1)', without affecting the triple bond. A novel cross-linked polyacetylene was synthesized from poly (1)' with [(nbd)RhC1](2)-Et3N catalyst.