The　coordination　environment　of　aluminum　species　plays　a　crucial　role　in　determining　the　catalytic　performance　of　zeolite-based　ammonia　selective　catalytic　reduction　(NH3-SCR)　catalysts.　Herein,　we　present　a　novel　strategy　to　boost　medium-　and　high-temperature　NH3-SCR　activity　through　the　employment　of　a　FeMOR　zeolite　enriched　with　distorted　tetra-coordinated　framework　Al　species　(denoted　as　Al(IV)-2).　The　obtained　FeMOR-K　demonstrates　outstanding　high-temperature　deNOx　performance,　achieving　a　wide　temperature　window　of　315–650　°C　with　a　90%　NOx　conversion.　Systematical　characterization　reveals　that　the　interaction　between　Fe　species　and　tetra-coordinated　framework　Al　species　(denoted　as　Al(IV)-1)　leads　to　transformation　of　Al(IV)-1　into　Al(IV)-2.　The　resulting　Al(IV)-2　species　enhance　the　dispersion　and　stability　of　iron　through　the　Fe-O-Al　bridging　structures　and　provide　additional　acidic　sites　for　NH3　adsorption,　thereby　facilitating　the　NH3-SCR　reaction　at　medium-　and　high　temperatures.　Kinetic　analysis　indicates　that　FeMOR-K　has　a　lower　activation　energy　compared　to　its　counterpart　with　less　Al(IV)-2　species.　Additionally,　ab　initio　molecular　dynamics　simulations　unveil　that　the　synergistic　anchoring　interaction　between　Al　and　Fe　species　governs　the　formation　of　Al(IV)-2　species　and　determines　the　final　state　of　Fe　species　in　the　catalyst.　This　comprehensive　understanding　of　the　relationship　between　the　distorted　tetra-coordinated　framework　Al　species　and　metal　active　sites　provides　new　insights　for　developing　superior　medium-　and　high-temperature　NH3-SCR　catalysts.　©　2025　Elsevier　Ltd