Aniline was mixed with thiophene and oxidized by ammonium persulfate in the presence of sulfuric acid via an aqueous polymerization pathway (PAT‐AP). Aqueous polymerization was also carried by sodium lauryl sulfate surfactant, and also by interfacial and electrochemical polymerization pathways. Polymers prepared were characterized by physical, spectral, and electrochemical methods. Nanofibers (30–60 nm diameter) was obtained in the case of aqueous polymerization pathway, whereas interfacial (40–60 nm) and electrochemical polymerization pathways show particulate (500–600 nm) morphology. Polymer samples were used as electrode materials in supercapacitor. Among the four different pathways, PAT‐AP nanofibers show higher capacitance of 614 F g−1 at 1 mV s−1. The values of specific capacitance, energy, and power densities of PAT‐AP were found to be 400 F g−1, 20 W h kg−1 and 1200 W kg−1, respectively, at a current density of 2 A g−1. The retention capacitance is 78% after completion of 1000 cycles. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42013.