The carbon direct electrochemical reactions in a solid oxide electrolyte direct carbon fuel cell (DCFC) are investigated experimentally with CH4-deposited carbon at the anode as fuel. The surface morphology of the anode cross-sections is characterized using a scanning electron microscope (SEM), the elemental distribution using an energy dispersive spectrometer (EDS) and an X-ray photoelectron spectroscopy (XPS), and the deposited carbon microstructures using a Raman spectrometer. The results indicate that all the carbon deposited on the yttrium-stabilized zirconium (YSZ) particle surfaces, the Ni particle surfaces, as well as the three-phase boundary, can participate in the electrochemical reactions during the fuel cell discharging. The direct electrochemical reactions for carbon require the two conditions that the O2- in the ionic conductor contact with a carbon reactive site and that the released electrons are conducted to the external circuit. The electrochemical reactions for the deposited carbon are most difficult on the Ni particle surfaces, easier on the YSZ particle surfaces and easiest at the three-phase boundary. Not all the carbon deposited in the anode participates in the direct electrochemical reactions. The deposited carbon and the O2- in the YSZ react to form the double-bonded adsorbed carbonyl group C = O. (C) 2010 Elsevier B.V. All rights reserved.