Characteristics of steam gasification and combustion of naphtha tar pitch, which is the bottom product of naphtha cracking process, were investigated by using the thermo gravimetric analyzer to develop the technology for obtaining syngas by using the naphtha tar pitch as a carbon source. Friedman’s and Ozawa-Flynn-Wall method were used to calculate activation energy, reaction order and frequency factor of reaction rate constant for both of steam gasification and combustion. The activation energy of combustion of naphtha tar pitch based on the fractional conversion by Friedman’s method was in the range of 41.58 ~ 68.14 kJ/g-mol when the fractional conversion level was in the range of 0.2~0.6, but 183.07~191.17 kJ/g-mol when the conversion level was 0.9~1.0, respectively. In case of steam gasification of naphtha tar pitch, the activation energy was in the range of 31.87~44.87 kJ/g-mol in the relatively lower conversion level (0.2~0.6), but 70.63~87.79 kJ/g-mol in the relatively higher conversion level (0.8~0.95), respectively. Those results exhibited that the steam gasification as well as combustion would occur by means of two steps such as devolitilization followed by combustion or gasification.