New series of C-60-derivatized bithiophenic precursors with low oxidation potential have been synthesized using the thiolate deprotection chemistry. The analysis of the electropolymerization of these compounds shows that the use of two-site precursors leads to polymers combining enhanced conjugation length, faster switching time, and improved stability under redox cycling. The unsuccessful attempts to identify the optical signature of the reduced forms of the attached C-60 by spectroelectrochemistry suggest that the PT backbone is unstable in the presence of the C-60 anion radical. Preliminary photoelectrochemical experiments on films deposited on platinum electrode reveal a significant enhancement of the photocurrent for the C-60-derivatized polymer when compared to a nonsubstituted reference polymer, indicating that these new materials are potentially useful for photovoltaic energy conversion.