Electrodeposition of conducting polyaniline (Pani) was made under potentiostatic condition at pH 1.0 in different electrolyte media (H2SO4 and HClO4) in the absence and presence of two organic dopants, disodium salts of naphthalene-1,5-disulphonic acid (NSA) and of catechol-3,5-disulphonic acid (CSA). The rate and yield of Pani deposition were dependent on the acid medium and the dopant employed. NSA in H2SO4 caused an increase in rate and yield but CSA decrease when compared to the rate and yield of H2SO4 alone. In HClO4 medium, both the dopants showed a decrease. With regard to DC electrical conductivity, both the dopants exhibited an enhancement in H2SO4 medium but NSA a decline in HClO4. Characterisation of the electrosynthesised polymer samples by various instrumental techniques (cyclic voltammetric: CV, FTIR, UV-Visible: UV-Vis, EPR, XRD, TGA and DTG methods) revealed that between the two acid media, H2SO4 was the better one. Further, it enlightened the role of two organic dopants in relation to the acid media. The advantageous role of NSA in H2SO4 had origin on its molecular characteristics such as non-polarity, larger pi-electron cloud etc., while CSA could not perform such a role because of its easily oxidisable hydroxyl groups. In HClO4, however, both the dopants could play only an unfavourable role owing to its greater polarity and oxidizing power than H2SO4, (C) 2003 Elsevier Science B.V. All rights reserved.