Conversion of waste to high-value products by pyrolysis is a suitable and harmless disposal technology for the abundant waste generated in the tobacco industry. To determine the optimum operational parameters for biomass pyrolytic polygeneration using tobacco waste as the feedstock, the product characteristics and nitrogen transformation were investigated from 250 to 950 degrees C. The highest low calorific values of gas and char were 13 MJ/m(3) at 750 degrees C and 15 MJ/kg at 450 degrees C, respectively. The optimum operating temperature recommended for biomass pyrolytic polygeneration of tobacco waste is 650 degrees C when the three products (char, oil, and gas) are balanced. The char formation process is divided into three stages: degradation (250-450 degrees C), reforming (450-650 degrees C), and condensation (>650 degrees C). Three types of N-containing structures are formed in chars: pyridinic N, pyrrolic/pyridine N, and quaternary N. Pyridinic N is dominant at low temperatures, whereas quaternary N becomes dominant at high temperatures. N-containing volatiles escape from chars with increasing temperature and are primarily found in oil below 550 degrees C and in gas above 650 degrees C. N-containing compounds are the major components (up to 45%) in the organic portion of oil, with pyridines, pyrroles, and piperidines as the dominant forms. In the gas product, NH3 and HCN are the major N-containing compounds released above 650 degrees C. This study is expected to be beneficial for the comprehensive utilization of tobacco waste.