NOx emission is a serious problem during fossil fuel combustion. Novel reburning fuels, namely, nitrogen-containing tar compounds, including pyridine and pyrrole were taken into consideration for NO reduction and investigated by quantum chemical method. Theoretical calculation results show that pyridine could first decompose into small species, such as CN and hydrocarbon radicals, then reduce NO to N₂. The decomposition of pyridine should overcome quite high energy barrier and adsorb a large amount of heat. This pathway may occur at high temperature zone, such as core flame zone of pulverized coal fired boiler. As soon as pyridine decomposes, the active intermediates (CN radical, etc.) could reduce NO very quickly. The direct reduction of NO by pyridine molecule should overcome lower energy barrier, which could occur at wider temperature range. Pyrrole is less thermostable than pyridine; the energy barriers of pyrrole cracking and direct reduction of NO stay at same level. Therefore, the reburning efficiency of pyrrole may be better at lower temperature than pyridine. Theoretical calculations indicate that nitrogen-containing tar compounds produced during biomass pyrolysis/gasification could have good performance for NO reduction in pulverized coal fired boiler as well as biomass or MSW furnace.