Electrodeposition of polyaniline (PAni) was performed across a broad pH range from pH 0.0 to 14.0. PAni films were found to grow from strong acidic environments at much faster rate and appeared to adopt different growth patterns from those grown from higher pH media, thus producing PAni films with very different morphologies ranging from nanofibres to microsized tubules to flakes like structures. The various morphologies of the PAni films were results of homogeneous and heterogeneous nucleation during electrochemical polymerization. These phenomena occurred under specific conditions which could be induced by varying the pH of the reaction media. Characteristic IR absorptions of the films deposited from increasing pH environment indicated little differences in chemical structure of the polymers except for the film grown from pH 14.0. Cyclic voltammetry data also indicated different electron transfer efficiency as a result of different morphology adopted. All except for PAni films obtained from pH 2.0 to 4.0 gave high specific capacitance at around 450Fg−1 in 0.5M H2SO4 and in 1.0M NaNO3 (pH 1.0) solution using 1.0mAcm−2 charging and discharging current density.