Crystallization of semi-crystalline polyaniline has been attempted by altering conditions such as nature of dopant acid and nature of oxidant by a one-pot chemical polymerization method. The samples were characterized by an array of analytical techniques. Highly ordered arrangement with sharp peaks was present in the X-ray powder diffraction pattern when ultrasonication of monomer solution was performed for 2 h before the addition of ammonium persulfate. The emeraldine salt form of PANI was confirmed for this sample from FTIR and Raman spectroscopy measurements. Thermal stability of this sample has been evaluated. Aggregation of ordered chains of PANI was evident in the SEM image. As the sample showed a BET surface area of 24.31 m(2)/g, its electrochemical behavior was determined by performing cyclic voltammetry and galvanostatic charge/discharge experiments. It was found to possess excellent electrochemical performances with a specific capacitance of 912.5 F g(-1) m(-1).