Photocatalytic　selective　organic　transformation　represents　an　emerging　avenue　for　artificial　photosynthesis　toward　renewable　solar　energy　conversion.　However,　solar-to-chemical　conversion　efficiency　in　photocatalysis　is　largely　hampered　by　the　sluggish　charge　transfer　kinetic　and　difficulty　in　precise　control　over　the　charge　migration　pathway.　Herein,　we　demonstrate　conceptually　new　metal–insulator–semiconductor　(MIS)　electron　tunneling　photosystems　to　finely　modulate　the　directional　charge　flow　for　photoredox　selective　organic　transformation.　The　ultrathin　insulating　organic　ligands　layers　capped　on　the　surfaces　of　metal　nanocrystals　(NYs)　and　transition　metal　chalcogenides　quantum　dots　(TMCs　QDs)　mutually　function　as　precise　directing-mediums　to　stimulate　spontaneous　electrostatic　self-assembly　between　the　tailor-made　oppositely　charged　metal　NYs　and　TMCs　QDs　for　constructing　metal　(Au,　Pd)　NYs/TMCs　(CdSe,　CdS)　QDs　heterostructured　electron　tunneling　photosystems.　The　electrons　photoexcited　from　TMCs　QDs　can　be　efficaciously　extracted　and　tunneled　to　metal　NYs　across　the　intermediate　insulating　hierarchical　ligands　layers　to　participate　in　the　photoredox　catalysis.　The　metal　NYs-insulating　ligands-TMCs　QDs　photosystems　can　efficiently　mediate　the　minority　carrier　transport　across　the　intermediate　insulating　ligand　layers　with　minimal　recombination,　thereby　resulting　in　the　significantly　enhanced　net　efficiency　of　multifarious　photoactivities　toward　selective　organic　transformation　including　anaerobic　photoreduction　of　nitroaromatics　to　amino　derivatives　and　selective　photo-oxidation　of　aromatic　alcohols　to　aldehydes　under　visible　light　irradiation.　The　ligand-triggered　electron　tunneling　effect　has　been　evidence　to　be　universal.　Our　work　would　inspire　ongoing　interest　in　exploring　diverse　organic　ligands-based　charge　tunneling　photosystems　and　provide　a　valuable　roadmap　for　substantial　solar　energy　conversion.　©　2021　Elsevier　Inc.