The HZSM-5 molecular sieves are a kind of special photocatalyst with photocatalytic activity, while their relationship between structure and function has been a matter of debate. Here, we report that for HZSM-5, the distinguished transformation of coordination environment derived from the removal of tetrahedral framework aluminium by thermal treatment will result in a considerable change in photocatalytic behaviours. The established NMR analysis combined with the theoretical calculations demonstrates the formation of extra-framework aluminium (EFAL) upon calcinations. This leads to a changed reaction path of photocatalytic oxidation of isopropyl alcohol in gas-phase over calcined HZSM-5 catalysts. DFT calculation results show the formed of EFAL species can increase the interaction energy between reactant molecules and zeolites which affords an outstanding photocatalytic reactivity and a controllable photocatalytic selectivity in the oxidation of isopropyl alcohol. This clearly indicates that the framework aluminium (FAL) species are responsible for acetone formation, while the EFAL species are apt to promote the deep mineralization of isopropyl alcohol to inorganic CO2. This study provides new understanding in the issue of photocatalysis for zeolite molecular sieves. (C) 2019 Elsevier Inc. All rights reserved.