The chemical synthesis of the copolymers poly(3-HT-co-EDOT-co-fluorene) and poly(3-HT-co-EDOT-co-TDR1) is reported. The first copolymer is derived of 3-hexylthiophene (3-HT), 3,4-ethylenedioxythiophene (EDOT) and 2,2'- (9,9-dioctyl-9H-fluorene-2,7-diyl) bisthiophene (fluorene). The second copolymer is derived of 3-hexylthiophene (3-HT), 3,4-ethylenedioxythiophene (EDOT) and (E)-2-(ethyl(4-((4-nitrophenyl)diazenyl)phenyl)amino)ethyl 2-(thiophen-3-yl)acetate (TDR1). Their physicochemical characterization by 1H NMR, FT-IR, DSC-TGA, GPC, UV-vis, cyclic voltammetry was carried out. These copolymers combine the high electron density and low oxidation potential of EDOT with the high charge mobility and processability of 3-HT. These are candidates for applications as active or barrier layer in electronic devices (bulk heterojuntion organic solar cells) or as functional membranes (e.g., sensors).