Conducting polymer synthesis of a new benzobisoxazole/thiophene derivative is reported. The conjugated co‐polymer presents the lowest bandgap (1.78 eV) reported for a neutral benzobisoxazole/thiophene polymer. Electrochemical polymerization is carried out by cyclic voltammetry, and the new conducting polymer is characterized by Raman spectroscopy and X‐ray photoelectron spectroscopy. The results indicate that the coupling of the monomer unit occurs at the 2,2′ positions of the thiophene ring. Theoretical studies in derivatives of this family of compounds are conducted to validate the effect on the bandgap modulation due to the change in the substituent on the phenyl moiety of the monomer. The comparison between experimental and theoretical properties shows the substituents impact on the optical properties of the system, and its viability to be used in sensors.