Polyamides containing thieno[2,3-b]thiophene moiety were prepared via a simple polycondensation reaction of the diaminothieno[2,3-b]thiophene monomer 1a with different kinds of diacid chlorides (including oxalyl, adipoyl, sebacoyl, isophthaloyl, terephthaloyl, 4,4′-azodibenzoyl, 3,3′-azodibenzoyl, p-phenylene diacryloyl) in the presence of LiCl and NMP as a solvent through low-temperature solution polycondensation. The chemical structures of model compound and synthesized polyamides were confirmed by FTIR, nuclear magnetic resonance spectroscopy (including 1H-NMR and 13C-NMR) and elemental analysis. In addition, the thermal stability, crystallinity structure and surface morphology of synthesized polyamides were characterized via thermogravametric analysis (TGA), wide-angle X-ray diffraction analysis (WAXD) and scanning electron microscopy (SEM). Also, the corrosion inhibition behavior of selected examples of polyamides was investigated; the inhibitive effect of the investigated polymers for carbon steel in 1.0 mol·L−1 HCl was studied using potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) methods. PDP results displayed that the polyamides containing thieno[2,3-b]thiophene moiety can be as mixed-type inhibitors. The inhibition efficiency (P, %) was found to be in the range from 67.13% to 96.01%. There is an increase in P by the synthesized polymers in comparison to the starting monomer. The adsorption of these polymers was found to obey Langmuir adsorption isotherm.