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　(lambda　＞=　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　photo　catalytic　activity　of　M53-RGO　toward　photo　catalytic　reactions.　Finally,　a　possible　photocatalytic　reaction　mechanism　is　also　investigated　in　detail.