In　this　work,　MIL-53(Fe)-reduced　graphene　oxide　(M53-RGO)　nanocomposites　have　been　successfully　fabricated　by　a　facile　and　efficient　electrostatic　self-assembly　strategy　for　improving　the　interfacial　contact　between　RGO　and　the　MIL-53(Fe).　Compared　with　D-M53-RGO　(direct　synthesis　of　MIL-53(Fe)-reduced　graphene　oxide　nanocomposites　via　one-pot　solvothermal　approach),　M53-RGO　nanocomposites　exhibit　improved　photocatalytic　activity　compared　with　the　D-M53-RGO　under　identical　experimental　conditions.　After　80　min　of　visible　light　illumination　(λ　≥　420　nm),　the　reduction　ratio　of　Cr(VI)　is　rapidly　increased　to　100%,　which　is　also　higher　than　that　of　reference　sample　(N-doped　TiO2).　More　significantly,　the　M53-RGO　nanocomposites　are　proven　to　perform　as　bifunctional　photocatalysts　with　considerable　activity　in　the　mixed　systems　(Cr(VI)/dyes)　under　visible　light,　which　made　it　a　potential　candidate　for　industrial　wastewater　treatment.　Combining　with　photoelectrochemical　analyses,　it　could　be　revealed　that　the　introduction　of　RGO　would　minimize　the　recombination　of　photogenerated　electron-hole　pairs.　Additionally,　the　effective　interfacial　contact　between　MIL-53(Fe)　and　RGO　surface　would　further　accelerate　the　transfer　of　photogenerated　electrons,　leading　to　the　enhancement　of　photocatalytic　activity　of　M53-RGO　toward　photocatalytic　reactions.　Finally,　a　possible　photocatalytic　reaction　mechanism　is　also　investigated　in　detail.　©　2015　American　Chemical　Society.