Micrometer-scale macroporous aluminosilicate catalyst was prepared via the sol-gel process. Results of catalytic cracking of 1,3,5-triisopropylbenzene showed that the synthesized aluminosilicate catalyst exhibited much higher activity than traditional ZSM-5 zeolite under the same condition. It is worth mentioning that the polymer product selectivity of aluminosilicate was much lower than that of ZSM-5, which might be useful for implementing the catalytic cracking process. The unique structure of macroporous aluminosilicate with interconnected-macropores and continuous skeletons was believed to be responsible for its excellent catalytic activity and low polymer product selectivity. Detailed discussion on the reaction pathway was also conducted.