Due to the several advantages of bulk heterojunction organic photovoltaics, such as low cost and high processability, many related materials containing electron donating and accepting moieties have been developed. In this aspect, we newly designed and synthesized the tetrathiafulvalene (TTF)-based main-chain polymer (6TTF-Polymer) and 6TTF-Polymer containing fullerene derivatives (6TTF-C60-Polymer) via maltonate coupling reaction and condensation polymerization. The electrochemical and optical properties of the 6TTF-Polymer were estimated by cyclic voltammetry, ultraviolet and photoluminescence spectroscopes. The high HOMO level (EHOMO = -4.79 Ev) and low band-gap energy (Eg = 1.91 eV) suggested that the 6TTF-Polymer could act as a good electron donor for the organic photovoltaic applications. This work was mainly supported by BK21 PLUS Program, Basic Science Research Program (2013R1A1A2007238) and Converging Research Center Program (2013K001428), Korea. D.-Y. Kim appreciates the support from Global Ph.D Fellowship Program (2013H1A2A1033907) and K.-U. Jeong acknowledges the support from LG Yonam Foundation.