Photocatalytic　hydroxylation　of　benzene　in　water　using　H2O2　as　the　oxidant　is　a　green　approach　toward　phenol　synthesis.　However,　the　immiscibility　of　benzene　in　water　results　in　poor　photocatalytic　performance　and　a　low　efficiency　of　H2O2　utilization.　To　enhance　drastically　the　affinity　between　the　aqueous　and　nonaqueous　phases,　an　amphiphilic　heterojunction　(Fe2O3/crystalline　carbon　nitride　(CCN))　has　been　synthesized　by　intimately　immobilizing　hematite　(Fe2O3)　nanoparticles　on　a　CCN　surface　for　the　photocatalytic　hydroxylation　of　benzene　to　phenol.　The　unique　amphiphilicity　of　Fe2O3/CCN　allows　the　formation　and　stabilization　of　homogeneous　emulsions　in　a　benzene/water　mixture　to　increase　the　effective　oil/water　interface　area　for　more　efficient　mass　transport.　Moreover,　the　well-established　type　II　heterojunction　between　Fe2O3　and　CCN　facilitates　the　fast　separation　and　transfer　of　photoelectrons　from　CCN　to　Fe2O3　for　the　photo-Fenton　activation　of　H2O2　with　high　utilization　efficiency.　We　recorded　a　maximum　phenol　conversion　of　31.6%　by　using　a　stoichiometric　amount　of　H2O2　(10　mmol)　on　the　photocatalytic　hydroxylation　of　benzene.　The　apparent　quantum　yield　of　phenol　production　at　lambda　=　420　nm　was　determined　to　be　47.1%.　This　amphiphilic　photocatalyst　approach　would　be　useful　for　realizing　other　advanced　oxidation　reactions　involving　immiscible　components.