A new copolymer derived from 2,7-carbazole with thiophene is reported. This copolymer was obtained through the synthesis of 2,7-dibromo-N-methyl carbazole and 2-bromothiophene using a Kumada-type reaction to bond both rings and using two different kinds of Pd catalysts, [Pd(OAc)2] and [Pd(PPh 3)4], with significant differences in their yields. The trimer that was obtained was subsequently electropolymerized using cyclic voltammetry, and the photoelectrochemical properties were determined. Polymerization using electrochemistry showed that the trimer contains two types of possible bonds for the formation of the macromolecule, which led to the formation of two distinctly different materials. The obtained materials exhibit promising photoelectric responses suggesting that they both can be explored in the designing of photovoltaic cells.