It is demonstrated that bifunctionalized polythiophenes involving thiol and azide end-functional groups can be synthesized by chain-growth Suzuki-Miyaura type polymerization. The bifunctionalized polythiophenes are successfully characterized by 1H NMR, gel permeation chromatography (GPC), and matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF). Furthermore, the azide end-group reacts with DNA via click chemistry to form a polythiophene/DNA hybrid structure, which is characterized by ESI-MS. The described synthetic approaches will lead to the synthesis of novel multi-block copolymers as well as biomolecule-based conjugated polymer structures.