In this study, both AlFe composite pillaring agents and AlFe pillared clays (AlFe-PILC) were synthesized via a facile process developed by our group, after which mixed Cr and Ce precursors were impregnated on AlFe-PILC. Catalytic combustion of organic pollutant chlorobenzene (CB) on CrCe/AlFe-PILC catalysts were systematically studied. AlFe-PILC displayed very high thermal stability and large BET surface area (SBET). After 4 h of calcination at 550 °C, the basal spacing (d001) and SBET of AlFe-PILC was still maintained at 1.91 nm and 318 m2/g, respectively. Large SBET and d001-value, along with the strong interaction between the carrier and active components, improved the adsorption/desorption of CB and O2. When the desorption temperatures of CB and O2 got closer to the CB combustion temperature, the CB conversion could be increased to a higher level. CB combustion on CrCe/AlFe-PILC catalyst was determined using a Langmuir–Hinshelwood mechanism. Adsorption/desorption/oxidation properties were critical to design highly efficient catalysts for CB degradation. Besides, CrCe/AlFe-PILC also displayed good durability for CB combustion, whether in a humid environment or in the presence of volatile organic compound (VOC), making the catalyst an excellent material for eliminating chlorinated VOCs.