The bee’s nest-like nanostructured CeO₂–Al₂O₃ powders were synthesized by combustion method using polyvinyl alcohol as a fuel and their catalytic activity were tested in the m-xylene and toluene combustion. The results showed that the catalytic reaction temperature increased monotonically from 200 to 250°C and from 250 to 300°C for the 90% conversion of m-xylene and toluene, respectively, with the calcination temperature in the range of 450–850°C. For both combustions, the sample calcined at 450°C with a bee’s nest-like nanostructure and average pore size of 800 nm exhibited the highest catalytic activity. Among the samples calcined at 850°C, the lowest catalytic reaction temperature for the 90% conversion of m-xylene and toluene of 250 and 300°C, respectively, was found with the sample having the equimolar ratio of Ce/Al.