We report the synthesis and characterization of a unique class of conjugated polymers, polytriacetyelenes (PTAs), from a set of trans-enediyne (EDY) monomers bearing alkyl and aromatic substituents. Two different methods, i.e., Glaser-Hay coupling and Pd-catalyzed oxidative coupling, were employed depending on the nature of the side-chains. Our methodology is highly versatile in that it allows direct attachment of aromatic substituents to the PTA main-chains, allowing enhanced tunability in polymer electronic properties, which has not been achievable through previously reported methods. The newly synthesized PTAs displayed strong ability of quenching the fluorescence of poly(3-hexylthiophene) (P3HT), a prototypical conjugated polymer in organic solar cells, indicating possible applications of these PTAs in optoelectronic devices. (C) 2015 Wiley Periodicals, Inc.