Photocatalytic　benzene　hydroxylation　reaction　using　a　clean　oxidant　such　as　H2O2　is　a　green　synthetic　approach　for　phenol　synthesis.　Here,　our　study　shows　that　silylated　iron　vanadate　(FeVO4)　nanorods　can　function　as　promising　photocatalysts　to　direct　hydroxylation　of　benzene　to　phenol,　by　taking　advantage　of　the　unique　benefits　of　covalently　bonded　organosilane　(OS)　groups　to　realize　kinetic　control　of　heterogeneous　photocatalytic　reactions.　The　grafting　of　OS　functional　groups　on　FeVO4　helps　to　tailor　its　surface　affinity　to　fine-tune　the　benzene　adsorption　behavior　and　photo-Fenton　process　for　H2O2　activation.　In　addition,　the　OS　groups　immobilized　on　the　FeVO4　surface　via　a　rather　strong　Si-O　bond　also　serve　as　an　effective　protective　coating　to　suppress　metal　leaching,　thus　affording　FeVO4　with　an　excellent　stability　to　undergo　a　heterogeneous　photo-Fenton　process.　As　a　result,　the　silylated　FeVO4　exhibits　robust　photocatalytic　benzene　hydroxylation　performance.　The　phenol　yield　and　selectivity　obtained　on　the　optimized　silylated　FeVO4　are　determined　to　be　20%　and　98%,　much　better　than　that　obtained　from　pristine　FeVO4.　Benefiting　from　its　robust　stability　and　tunable　surface　affinity,　the　silylated　FeVO4　will　have　broad　applications　in　photocatalytic　selective　oxidation　to　produce　fine　chemicals.　©　The　Royal　Society　of　Chemistry.