Galvanostatic electrodeposition techniques were applied for the preparation of novel electroactive manganese oxide electrodes. The effects of supersaturation ratio on the morphology and crystal structure of electrodeposited manganese oxide were studied. Manganese oxide electrodes were synthesized by anodic deposition from acetate-containing aqueous solutions on Au coated Si substrates through the control of nucleation and growth processes. By changing deposition parameters, a series of nanocrystalline manganese oxide electrodes with various morphologies (continuous coatings, rod-like structures, aggregated rods and thin sheets) and an antifluorite-type crystal structure was obtained. Detailed chemical and microstructural characterization of as-deposited electrodes was conducted using SEM, TEM and AAS. Manganese oxide thin sheets show instantaneous nucleation and single crystalline growth, rods have a mix of instantaneous/progressive nucleation and polycrystalline growth and continuous coatings form by progressive nucleation and polycrystalline growth. In addition, the electrochemical behavior was investigated by cyclic voltammetry. The experimental results show that manganese oxide electrodes, with rod-like and thin sheet morphology, exhibited enhanced electrochemical performance. The highest specific capacitance (similar to 230 F g(-1)) and capacitance retention rates (similar to 88%) were obtained for manganese oxide thin sheets after 250 cycles in 0.5 M Na(2)SO(4) at 20 mV s(-1). (C) 2011 Elsevier B.V. All rights reserved.