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With the concern of future energy use, hydrogen is taken as an important role in energy alternatives. In addition, biomass air gasification by using fluidized bed is an efficient and advanced method for hydrogen production. Despite of energy product generation, some pollutants such as PAHs easily formed in gasification process because of tar decomposition. Accordingly, this study provides a fundamental work of emission behavior of PAHs generated under different operating conditions such as temperature, air factor, and addition of catalysts. The experimental result shows the emission concentration of PAHs decreases with the operating temperature increases, but PAHs increases with increasing of air factor. Besides, addition of CaO resulting a reduce influence on PAHs emission, but Al2O3 added in fluidized bed cause bimodal particle size segregate and reduce fluidized bed quality that leads PAHs formation during biomass air gasification.