The Fe/ZSM-5 catalyst was prepared and used for fast pyrolysis of biomass to aromatic hydrocarbons by pyrolysis-gas chromatography/mass spectrometry experiments (Py-GC/MS). It was found that the Fe/ZSM-5 catalyst demonstrated better activity in the conversion of oxygenates and formation of monocyclic aromatic hydrocarbons (MAHs) than the ZSM-5 catalyst. Furthermore, for catalytic fast pyrolysis of biomass with Fe/ZSM-5 catalyst, the yields of aromatic hydrocarbons were significantly increased with the rise of temperature from 500 °C to 600 °C, and then decreased with the increase of temperature from 600 °C to 800 °C. Based on the results of catalyst characterization and activity experiments, it seems that the Fe/ZSM-5 catalyst maintained the structure of ZSM-5, and the incorporation of Fe into ZSM-5 zeolites contributed to the formation of MAHs and simultaneously hindered the further polymerization reaction of MAHs and other oxygenates.