Supported catalysts were prepared with CeCl 3 and CeO 2 as active components, the catalytic degradation of volatiles from pine particle pyrolysis was studied. Activated alumina was used as the carrier of CeO 2 and CeCl 3 to prepare CeO 2 /Al 2 O 3 and CeCl 3 /Al 2 O 3 catalysts. Experimental results show that the two catalysts can effectively reduce the yield of pyrolysis liquid-phase products and markedly increase the yield of gas-phase products. Compared with no catalyst, the liquid product yield decreased by 25.69% and the pyrolysis gas yield increased by 29.48% at a pyrolysis temperature of 650 °C by using CeO 2 /Al 2 O 3 catalyst. The active components in CeO 2 reduced the volume fraction of C n H m in pyrolysis gas and increased the volume fraction of H 2 . Under the catalysis of CeCl 3 /Al 2 O 3 , the CO content and the low calorific value of the product gas increases. The addition of the two catalysts cracked the oxygen-containing functional groups in the tar to various extents, reducing the tar yield and increasing the pyrolysis gas yield. For the simple reduction of tar yield in pyrolysis gas, the catalytic cracking effect of CeO 2 /Al 2 O 3 catalyst was better than that of CeCl 3 /Al 2 O 3 catalyst, and CeCl 3 /Al 2 O 3 catalyst should be selected when degrading tar while obtaining a relatively high low heating value.