Metal-organic　frameworks　(MOFs),　with　their　high　specific　surface　area,　excellent　stability　and　high　electron　transfer　ability,　are　ideal　supports　for　accommodating　single　metal　atoms.　However,　the　low　utilisation　of　single-atom　active　sites　limits　the　improvement　of　oxygen　reduction　reaction　(ORR)　performance.　In　this　work,　NH2-MIL-53(Al),　a　MOF　possessing　a　mesoporous　cage　architecture,　is　used　as　the　precursor　to　prepare　N-doped　carbon　supports　(denoted　herein　as　N-HPC)　with　a　well-defined　mesoporous　structure　through　pyrolysis.　Thiourea　was　further　employed　for　S　doping　and　impregnated　with　a　FePc,　and　heated　again　to　yield　Fe@S/N-HPC　catalysts　rich　in　accessible　FeNx　single　atom　sites.　The　porous　structure　is　more　accessible　to　Fe　center　atoms　by　exposing　the　active　sites,　provide　easy　electron　conductivity　and　facilitate　mass　transport　of　ORR-intermediates.　The　prepared　hierarchically　porous　architecture　of　NH2-MIL-53(Al)-derived　and　S　induced　electron　localization　of　Fe　SAs　sites　exhibit　excellent　ORR　performance　in　alkaline　(E1/2　=　0.88　V)　medium.　©　2024　Elsevier　B.V.