The　photocatalytic　activity　for　benzene　hydroxylation　to　phenol　by　hydrogen　peroxide　has　been　evaluated　using　a　series　of　photocatalysts　based　on　defective　graphene.　The　series　includes　defective　graphene　containing　or　not　Au　and　Cu2O　nanoparticles.　The　latter　exhibits　the　highest　activity,　but　a　very　low　phenol　yield　as　a　consequence　of　the　occurrence　of　a　large　degree　of　mineralization.　A　considerable　increase　in　phenol　selectivity　was　achieved　by　modifying　the　surface　of　the　Cu2O　nanoparticles　supported　on　defective　graphene　with　long-chain　alkanethiols.　Under　the　optimal　conditions　using　an　octanethiol-modified　Cu2O-graphene　photocatalyst,　a　selectivity　to　phenol　of　about　64%　at　30%　benzene　conversion　was　achieved.　This　remarkable　selectivity　was　proposed　to　derive　from　the　larger　hydrophobicity　of　the　alkanethiol-modified　Cu2O-graphene　photocatalyst　that　favors　the　preferential　benzene　adsorption　versus　adsorption　of　phenol　and　hydroxybenzenes.　©　2018　The　Royal　Society　of　Chemistry.