The Fe/CaO catalysts with different Fe contents were prepared and used for fast pyrolysis of sawdust by Py-GC/MS experiments. The effects of Fe contents of the Fe/CaO catalysts on the yields and compositions of pyrolytic products were studied. It was found that when Fe contents changed from 5% to 15% (wt.), more Ca 2 Fe 2 O 5 phases were formed on the Fe/CaO catalysts, and all the catalysts were effective in upgrading the bio-oils, but the catalytic activities were gradually inhibited with the increase of Fe contents. Among the three catalysts, the 5Fe/CaO catalyst displayed the best activity in reducing the oxygenated compounds, which is beneficial for the improvement of the properties of bio-oils used as liquid fuels.