Effect of inherent volatile matters in fuels on electrochemical reactions of anode was investigated for a single direct carbon fuel cell (DCFC). Raw coals used as power source in the DCFC release light gases into the atmosphere under the operating temperature of DCFC ($700^{circ}C$) by thermal decomposition and only char remained. These exhausted gases change the gas composition around anode and affect the electrochemical oxidation reaction of system. To investigate the effect of produced gases, comparative study was conducted between Indonesian sub-bituminous coal and its char obtained through thermal treatment, carbonizing. Maximum power density of raw coal ($52mW/cm^2$) was appeared higher than that of char ($37mW/cm^2$) because the gases produced from the raw coal during thermal decomposition gave additional positive results to electrochemical reaction of the system. The produced gases from coals were analyzed using TGA and FT-IR. The influence of volatile matters on anodic electrolyteelectrode interface was observed by the equivalent circuit induced from fitting of impedance spectroscopy data.