Iron-containing　heterogeneous　catalysts　hold　great　promising　for　the　direct　hydroxylation　of　benzene　to　phenol.　However,　their　catalytic　performance　is　greatly　hampered　by　the　inherent　drawbacks　of　iron-containing　solids,　in　particular　their　hydrophilic　surface　structure　and　inevitable　leaching　of　iron　species　during　the　Fenton　process,　which　result　in　poor　selectivity　and　durability　toward　phenol　production.　Herein,　we　demonstrate　that　the　encapsulation　of　iron　nanoparticles　with　N-doped　carbon　layer　as　core-shell　nanostructures　(Fe@NC)　is　a　promising　synthetic　strategy　to　advance　iron-containing　solids　for　benzene　hydroxylation.　The　rigid　carbon　shells　conformably　coating　on　iron　cores　not　only　protect　iron　from　leaching　but　also　facilitate　the　selective　adsorption　of　benzene　molecules　on　Fe@NC　because　of　their　excellent　stability　against　acid　etching　and　hydrophobic　surface　with　the　unique　π-conjugated　electron　system.　As　a　result,　Fe@NC　exhibit　a　robust　catalytic　durability　and　good　yield　with　high　selectivity　for　the　direct　hydroxylation　of　benzene　to　phenol.　Benefiting　from　their　unique　core-shell　nanostructures　and　strong　host-guest　electron　interaction　between　metals　and　carbons,　Fe@NC　are　expected　to　be　promising　also　for　other　liquid-phase　organic　synthesis.　Copyright　©　2020　American　Chemical　Society.