Phenol　is　one　of　the　most　important　chemicals　in　industry.　One-step　selective　benzene　hydroxylation　is　an　attractive　yet　challenging　method　for　phenol　production,　especially　when　such　a　reaction　can　be　driven　by　solar　energy.　Herein,　we　reported　that　a　highly　selective　benzene　hydroxylation　to　phenol　can　be　achieved　over　two　Fe-based　metal　organic　frameworks　[MIL-100(Fe)　and　MIL-68(Fe)]　under　visible　light　irradiations　using　hydrogen　peroxide　(H2O2)　as　an　oxidant.　An　optimal　benzene　conversion　of　30.6%　was　achieved　with　a　H2O2:benzene　ratio　of　3:4　over　MIL-100(Fe)　after　24　h　irradiations.　ESR　results　and　the　kinetic　studies　suggested　that　a　successful　coupling　of　the　photocatalysis　of　Fe-O　clusters　in　Fe-based　metal　organic　frameworks　(MOFs)　with　a　Fenton-like　route　is　involved　in　this　benzene　hydroxylation　process.　The　comparison　of　the　reaction　over　MIL-100(Fe)　and　MIL-68(Fe)　reveals　that　the　structure　of　MOFs　significantly　influences　the　photocatalytic　efficiency.　Because　the　composition　and　the　structure　of　MOFs　are　highly　tunable,　this　study　highlights　the　great　potential　of　using　Fe-based　MOFs　for　photocatalytic　benzene　hydroxylation　to　form　phenol,　which　may　result　in　an　economical,　sustainable,　and　thus　green　process　for　phenol　production.