Abstract: In order to realize the efficient utiliation of low rank coal, taking the Fe2O3/CaO as hybrid catalyst, the pyrolysis behaviors of coasl sampls from Zihecaogou Mine and Datong . Mining Area respetively were investigated by thermogravimetry deviece under different dosage of hybrid catalyst. The catalytic mechanism was discussed from the kinetic analysis and gas co . mposition. The results showed that Fe2O3/CaO could affect the pyrolysis of coal, and had different effects on different coals. The activation energy and pyrolysis temperature range decreased with the addition of catalyst, which make the reaction easier. Meanwhile, the gas compositions had obviously changed, it can promote the escape of volatile components, and the cracking and condensation reactions of coal samples could be carried out more easily. The excessive Fe2O3/CaO hybrid catalyst's addition had inhibitory effect on coal pyrolysis, with the addition of mass f raction 5% of Fe2O3/CaO, the best catalytic effects were observed for the pyrolysis of coals.