Selective　one-step　benzene　hydroxylation　to　produce　phenol　is　a　green　process,　especially　when　the　reaction　can　be　carried　out　in　water　using　economical　carbon　materials　as　catalysts　under　visible　light.　Herein,　we　reported　that　hydroxylation　of　benzene　can　be　realized　over　reduced　graphene　oxide　(RGO)　in　water　under　visible　light　using　H2O2　as　an　oxidant.　By　engineering　the　surface　wettability　of　RGO　from　hydrophilic　(with　a　contact　angle　of　52　degrees)　to　hydrophobic　(with　a　contact　angle　of　127　degrees),　the　performance　for　benzene　hydroxylation　can　be　significantly　improved　by　more　than　three　times.　An　optimum　conversion　of　benzene　reached　3.1%　with　a　H2O2/benzene　ratio　of　1:1　over　hydrophobic　RGO　after　irradiation　for　20　h.　The　catalyst　can　be　facilely　recycled,　and　no　obvious　decrease　in　the　activity　was　observed　after　four　successive　runs.　This　study　provides　a　green　and　sustainable　method　for　phenol　production　based　on　economical　carbon　materials　and　also　highlights　the　important　role　of　RGO　as　a　promising　photocatalyst　for　organic　syntheses.