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Abstract This study introduces a benzodithiophene‐S,S‐tetraoxide (BDTT) monomer as an acceptor and 3,4‐ethylenedioxythiophene flanked thiophene (TEDOT₂) and terthiophene (T₃) as donor molecules for polymer formation. The synthesis of thepoly(TEDOT₂‐BDTT)andpoly(T₃‐BDTT)copolymers was performed via a single‐step monomer radical formation that is typically associated with electropolymerization methods. The electropolymerization is controlled by using a suitable monomer stoichiometric ratio that enables the deposition of copolymer thin films on the working electrode. Resultant copolymers were investigated by electrochemical analysis and their electronic properties are discussed in detail. A low average electron transport resistance of 16.5 Ω was found forpoly(TEDOT₂‐BDTT), indicating excellent conductive behavior. Solid‐state absorbance and emission studies of the copolymers show visible to near‐infrared spectral activity. Results support an effective strategy towards highly efficient electronically conducting polymers (ECPs) based on a unique BDTT monomer.