The　catalytic　dehydration　of　glycerol　to　acrolein　offers　a　sustainable　route　for　efficiently　utilizing　low-cost　and　renewable　bioglycerol.　This　work　deeply　explores　glycerol　dehydration　to　acrolein　over　ZSM-5　zeolite　catalysts　with　various　pore　structures　and　aluminum　distributions.　The　results　reveal　that　glycerol　conversion　is　enhanced　through　the　construction　of　a　mesoporous　structure　and　the　increase　in　Br　&　oslash;nsted　acid　sites　of　the　catalysts,　but　acrolein　selectivity　is　not　directly　related　to　these　factors.　Further　characterizations,　density　functional　theory　calculation,　kinetic　study,　and　reaction　mechanism　analysis　demonstrate　that　the　richest　Alsingle　sites　in　the　zeolite　framework　and　the　least　Alpair　sites　in　the　straight　and　sinusoidal　channels　can　prevent　the　generated　acrolein　from　adsorbing　on　adjacent　Al　sites.　This　allows　acrolein　to　immediately　escape　from　the　catalyst　surface,　reducing　side　reactions　and　enhancing　its　selectivity.　Therefore,　the　synergistic　between　the　mesoporous　structure　and　more　Alsingle　sites　in　the　ZSM-5　zeolite　framework　promotes　acrolein　yield.　Additionally,　a　descriptor　phi,　reflecting　the　amount　of　Alsingle　sites　and　the　external　specific　surface　area　of　the　ZSM-5　zeolite,　is　first　proposed　to　more　clearly　elucidate　the　structure-performance　relationship.　This　study　provides　a　new　perspective　for　understanding　the　mechanism　of　catalytic　dehydration　of　glycerol　to　acrolein,　guiding　the　development　of　highly　efficient　catalysts.　It　is　significant　for　the　sustainable　development　of　the　biodiesel　and　acrolein　production　industry.