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.　©　2019　Elsevier　Inc.