Selective　hydroxylation　of　benzene　to　phenol　over　a　visible　light　driven　photocatalyst　is　a　sustainable　approach　for　the　green　synthesis　of　phenol.　Iron　vanadate　(FeVO4)　nanorods　with　an　intrinsic　photo-Fenton　catalytic　behavior　toward　H2O2　activation　is　a　promising　candidate　photocatalyst　for　the　benzene　hydroxylation　reaction;　however,　its　photocatalytic　performance　was　greatly　limited　by　the　serious　leaching　of　metals　during　the　hydroxylation　process.　Herein,　it　has　been　demonstrated　that　this　issue　can　be　well　addressed　by　the　conformably　coating　of　FeVO4　nanorods　with　an　atomically-precise　thickness　controlled　dense　Al2O3　layer　(FeVO4@Al2O3)　through　the　atomic　layer　deposition　(ALD)　technology.　The　Al2O3　nanolayer　can　well　protect　the　FeVO4　nanorods　from　directly　contacting　with　the　reaction　solution,　thus　effectively　suppressing　the　leaching　of　metals　during　the　photocatalytic　hydroxylation　process.　In　addition,　the　Al2O3　coating　on　FeVO4　also　facilitates　the　kinetic　control　of　heterogeneous　benzene　hydroxylation　reaction　over　the　catalyst　surface,　such　as　the　benzene　adsorption　behavior　and　the　photo-Fenton　activation　of　H2O2.　As　a　result,　FeVO4@Al2O3　exhibited　an　enhanced　photocatalytic　performance　with　a　good　durability　in　the　long-term　production　of　phenol.　©　2022　Wiley-VCH　GmbH.