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In this study, aniline-based monomer, N,N′-(propane-1,3-diyl)bis(2-aminobenzamide), (PAB), was synthesized and characterized by proton nuclear magnetic resonance (1H-NMR), carbon-13 nuclear magnetic resonance (13C-NMR), and Fourier transform infrared spectroscopy. The electropolymerization of the monomer was performed on glassy carbon electrode by cyclic voltammetry (CV). The effects of solvent, dopant, scan number, and scan rate on the electropolymerization and properties of the poly(PAB) films were investigated. The modified electrode was also characterized by Fourier transform infrared-attenuated total reflection spectroscopy and scanning electron microscopy–energy-dispersive X-ray analysis. The capacitive properties of the poly(PAB) films were firstly tested by electrochemical impedance spectroscopy. The highest specific capacitances (Csp) of poly(PAB) films were obtained as Csp = 6.22 mF cm−2 in 0.1 M lithium perchlorate/acetonitrile (ACN) for [PAB]0 = 20 mmol dm−3 and Csp = 16.9 mF cm−2 in 1 mol dm−3 sulfuric acid for [PAB]0 = 5 mmol dm−3 at the scan rate of 5 mV s−1 from CV measurements. This study is novel because it was the first study on capacitance performances of poly(PAB) films in the literature.