The electropolymerization of pyrrole (Py), 3-(4-tert-butylphenyl)thiophene (TPT) monomer or the mixed Py and TPT monomers on stainless steel mesh substrate were performed in 1 M LiClO4/acetonitrile solution. A much lower potential of 0.75 V was required for the co-electropolymerization of Py and TPT, in sharp contrast to that of 1.20 V for poly(3-(4-tert-butylphenyl)thiophene) (PTPT) formation. The resultant homopolymers and copolymer were characterized with FESEM and FTIR, and assembled into supercapacitors to investigate their electrochemical performances. The copolymer electrode delivered the highest specific capacitance of 291 F g−1 at a scan rate of 5 mV s−1, in comparison with that of 216 and 26 F g−1 for PPy and PTPT, respectively. This copolymer also exhibited a greatly improved cycling stability – only 9% of capacitance decrease was observed after 1000 charging–discharging cycles at a current density of 5 A g−1, while the capacitance losses for PPy and PTPT were 16% and 60%, respectively.