Substituted polyacetylenes with alkylphenyl side groups and head-to-head regioregularity were prepared through anionic living polymerization of template monomers Poly or and subsequent dehydrogenation process. The template monomers have the structure of 2,3-disubstituted-1,3-butadienes prepared by palladium-catalyzed Kumada coupling of the corresponding vinyl bromides. Anionic polymerizations of the template monomers produced narrow disperse substituted polybutadiene precursors with exclusive 1,4-enchainment. The precursors were converted into soluble polyacetylene derivatives via two methods, e.g., bromination followed by elimination of HBr, and direct dehydrogenation by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), both resulting in dark colored products with significant red shift in UV spectra. The obtained head-to-head polyacetylene derivatives exhibited highly thermal stability, possibly due to trans-rich and/or head-to-head chain configurations. The microstructures of the poly(2,3-diallcylphenyl butadiene) precursors were analyzed in detail using NMR spectroscopy with regard to the solvent effect during polymerization. Block copolymers containing substituted polyacetylene segments were prepared through sequential anionic polymerization of different monomers, followed by dehydrogenation transformation. The present synthesis may serve as a new strategy for tailoring molecular structures of polyacetylene-based polymers by virtue of anionic living polymerization techniques.