The present paper discusses synthesis and characterization of MnO2, poly-aniline (PANI) and PANI/MnO2 thin films on stainless steel substrates (SS) for electrochemical supercapacitor applications. The MnO2 thin films are formed using galvano-static electrodeposition of Mn, following electrochemical oxidation in a KOH bath. PANI and PANI/MnO2 layered thin films are also prepared via electrochemical polymerization and electrodeposition techniques. The thin films are investigated for their structural and morphological studies. Further, the electrochemical super-capacitive properties are probed using cyclic voltametry (CV), galvano-static charging-discharging and electrochemical impedance spectroscopy (EIS) techniques. The layered PANI/MnO2 has shown a significant increase in voltage window and consequently the specific energy and power over parent MnO2 electrode. (C) 2014 Elsevier Ltd. All rights reserved.