Two-dimensional　(2D)　transition　metal　carbide,　known　as　MXene,　has　recently　received　enduring　atten-tion　for　solar　energy　conversion　by　virtue　of　its　pivotal　role　as　efficient　interfacial　charge　transfer　mediator　for　photocatalysis.　However,　controllable　design　of　MXene-based　heterostructured　photosystems　is　still　in　the　infant　stage　and　MXene-dominated　photoredox　mechanism　in　photoredox　selective　organic　catalysis　has　so　far　not　yet　been　unleashed.　Herein,　we　conceptually　report　the　rational　construction　of　2D/2D　heterostructures　by　a　facile　electrostatic　self-assembly　approach　utilizing　oppositely　charged　transition　metal　chalcogenides　(TMCs:　CdIn2S4,　CdS,　Zn0.5Cd0.5S,　ZnIn2S4)　nanosheets　(NSs)　and　Ti3C2Tx　(MXene)　as　the　building　blocks　for　photocatalytic　selective　organic　transformation.　The　peculiar　faceto-face　stacking　mode　between　the　building　blocks　and　suitable　energy　level　alignment　synergistically　endow　the　MXene-TMCs　NSs　heterostructures　with　markedly　enhanced　photoactivities　toward　multifarious　photoredox　catalysis　including　anaerobic　selective　photoreduction　of　nitroaromatics　to　amino　derivatives　and　photoxidation　of　aromatic　alcohols　to　aldehydes　under　the　irradiation　of　visible　light.　The　considerably　enhanced　photoactivities　of　MXene-TMCs　NSs　heterostructures　are　caused　by　the　integrated　merits　of　Ti3C2Tx　(MXene)　including:　(i)　abundant　hydrophilic　groups　on　the　Ti3C2Tx　(MXene)　surface　for　affording　substantial　interaction　with　TMCs　NSs,　which　benefits　the　charge　migration;　(ii)　strong　redox　activities　of　surface　Ti　sites　which　promotes　multiple　electron　reduction;　(iii)　electrons　withdrawing　capability　of　Ti3C2Tx　(MXene)　to　boost　the　electron　transfer　from　TMCs　NS　to　Ti3C2Tx　(MXene),　thereby　enhancing　the　charge　separation.　This　work　would　open　a　new　frontier　for　constructing　a　host　of　MXene-based　heterostructured　photosystems　and　unveiling　the　charge　transfer　mechanism　of　MXene　for　solar　energy　conversion.　(c)　2020　Elsevier　Inc.　All　rights　reserved.