Plasma carbon blacks of 20~30 nm diameter were synthesized by direct decomposition of natural gas using a hybrid plasma torch system with 50 kW direct current and 4 MHz of radio frequency. The insulating rector which inside diameter of 400 mm and length of 1500 mm, respectively was kept at 300~400℃ during the preparation. The ultimate analysis of plasma carbon blacks reveals that the raw plasma carbon blacks contains a large quantity of volatile which is mainly consist of hydrogen. Therefore devolatilization of raw plasma carbon blacks were carried out at 900℃ for one hour under nitrogen atmosphere. The devolatilization leads to the decrease in electrical resistivity and surface oxygen functional groups of plasma carbon black significantly. In order to investigate the plasma carbon as a catalyst support, devolatilized plasma black at 900℃ (DPB) supported PtAu catalyst was synthesized by sodium boronhydride reduction method. Electrochemical measurements and direct formic acid fuel cell test indicated that catalytic activity of DPB supported PtAu catalyst for formic acid oxidation was similar to that of Vulcan XC-72 of commercial carbon black supported one.