Electroactive random copolymers of 3,4-Propylenedioxythiophene (ProDOT) and N-Phenylsulfonyl Pyrrole (PSP) were electrochemically synthesized on single carbon fiber microelectrode (SCFME) by cyclic voltammetry (CV). Fourier Transform Infrared-Attenuated Total Reflectance (FTIR-ATR) measurements indicate the inclusion of PSP into the copolymer structure. The influence of feed ratios on the copolymers was studied by CV and electrochemical impedance spectroscopy (EIS) and equivalent circuit modelling (ECM). The morphologies and film thicknesses of copolymers were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results have shown that the principal changes in morphology, conductivity, porous nature and thickness of Poly(ProDOT-co-PSP) film depend on the concentration of PSP. The strong electron-withdrawing sulfonyl group substitution on PSP significantly inhibited electrochemical copolymerization. Semicircular characteristics at Nyquist plots reflected an increasing trend with the increase of PSP concentration in the feed at high frequency. The semicircular characteristic of the copolymer film is useful for the bioelectrochemical sensor applications.