Conjugated poly(3-hexylthiophene) copolymer derivatives containing 10% appended porphyrin moieties are prepared using a supramolecular approach toward applications in organic electro-nics. The self-assembled polythiophene-porphyrin copolymers are synthesized by coordination of the porphyrinato central zinc ions to the imidazole-functionalized polythiophene side chains. Evidence for the self-assembly process is provided by 1H NMR spectroscopy, single crystal X-ray diffraction, and optical absorption studies on model compounds. The polythiophene-porphyrin copolymers show an extended absorption window in the region of 420-650 nm due to the contribution of the porphyrin. Photoluminescence studies indicate concentration-dependent energy transfer from P3HT to the porphyrin. Preliminary photovoltaic studies are performed by combining the polythiophene-porphyrin copolymers with PC61BM in the photo-active layer of bulk heterojunction organic solar cells. Porphyrin-functionalized poly(3-hexy-lthiophene) copolymers are prepared through a supramolecular metal coordination approach.