Abstract Coal seam pyrolysis occurs during coal seam fires and during underground coal gasification. This is an important source of polycyclic aromatic hydrocarbon (PAH) emission in China. Pyrolysis in a coal seam was simulated in a tubular furnace. The 16 US Environmental Protection Agency priority controlled PAHs were analyzed by HPLC. The effects of temperature, heating rate, pyrolysis atmosphere, and coal size were investigated. The results indicate that the 3-ring PAHs AcP and AcPy are the main species in the pyrolysis gas. The 2-ring NaP and the 4-ring Pyr are also of concern. Increasing temperature caused the total PAH yield to go through a minimum. The lowest value was obtained at the temperature of 600 °C. Higher heating rates promote PAH formation, especially formation of the lower molecular weight PAHs. The typical heating rate in a coal seam, 5 °C/min, results in intermediate yields of PAHs. The total PAHs yield in an atmosphere of N 2 is about 1.81 times that seen without added N 2, which indicates that an air flow through the coal seam accelerates the formation of PAHs. An increase in coal particle size reduces the total PAHs emission but promotes the formation of 5- and 6-ring PAHs.