Microwave pyrolysis of SF6 on alumina-based catalyst doped with cerium sulfate was investigated. Silicon Carbide (SiC) used as a microwave susceptor. The catalysts were characterized by X-ray diffraction (XRD) and the destruction and removal efficiency (DRE) of SF6 was evaluated by GC-TCD. We found that the optimal cerium content was 20wt% at microwave pyrolysis of SF6. The catalysts modified by cerium showed higher DRE at lower reaction temperature compared with original catalysts. The highest DRE of SF6 on CeA (20) was 80% at 600oC reaction temperature and the DRE was up to 95% when the reaction temperature over 700oC. It showed the alumina-based with cerium promotes the removal efficiency of SF6 at a mild reaction temperature. From XRD results, modified catalysts could be higher stability because of no transformation of the crystal phase after reaction.