We developed a novel series of palygorskite-SO42 −/ZnAl2O4 composites. Palygorskite played a key role in improving the catalytic performance of the samples. Palygorskite-SO42 −/ZnAl2O4 composites showed the higher catalytic activities compared with SO42 −/ZnAl2O4. Palygorskite/ZnAl2O4 ratio essentially affected the structures and catalytic performance. Palygorskite-SO42 −/ZnAl2O4 (1:1) showed the higher catalytic activities as well as the better reusability.