Direct syntheses of carbon structures including nanodiamond, microdiamond and diamond-like carbon (DLC) on silicon wafers by liquid phase electro-deposition are presented. The solution (ethanol/water) was employed as electrolyte at different concentration levels. Assays were carried out maintaining constant the electric potential between the silicon electrodes in the range of (80-300 V) at current density of approximately 2.0 mA/cm(2). Scanning electron microscopy showed that non-uniform, smooth and heterogeneous structures were produced. The structural composition was evaluated by micro-Raman spectroscopy. A mechanism for the formation of sp(3) and sp(2) hybridizations is proposed. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.066203jes] All rights reserved.