In this study, gasification experiments were conducted using high calorific waste by measuring flue gas and gaseous pollutant composition. The feedstock used in this experiment was collected from industrial wastes and had a heating value more than 5,000 kcal/kg as well as low moisture and ash contents. Experiments were conducted at 1,200°C temperature by changing equivalent ratios (ERs) to find out an optimum condition for syngas production. Results showed that at ER 0.3, the highest syngas composition (around 81%) was obtained in flue gas. In this study, gas pollutant was sampled in cold absorbent by following Korean air pollutant standard sampling method. Later, sampled solutions were analyzed by IC (Ion Chromatography) to find out gaseous pollutant concentration. Usually, after gas cleanup system, all of the gaseous pollutants are removed by wet scrubber and catalyst reactor. However, in this study, due to gaseous pollutants removed by wet scrubber, the removal efficiency of gaseous pollutants showed lower performance compared with other catalyst clean up system. Thus, it is advisable to install a cleaning unit to deal with tar and soot.