Inspired　by　the　concept　of　frustrated　Lewis　pairs　(FLPs)　from　homogeneous　catalysis,　an　organic　supramolecular　bridged　metal-organic　frameworks　(MOFs)　heterojunction,　i.e.,　a　perylene-3,4,9,10-tetracarboxylic　diimide@MIL-125(Ti)-NH2　(denoted　PDI@MTi)　composite　is　successfully　fabricated　via　a　two-step　synthesis　method.　Experimental　characterisations　and　theoretical　calculations　reveal　that　in　the　obtained　“TiO5−x-ligand-PDI”　FLPs,　the　unsaturated　Ti-O　clusters　function　as　a　Lewis　acid　to　accept　photogenerated　electrons,　and　the　PDI　sites　act　as　a　Lewis　base　to　capture　photogenerated　holes.　With　the　unique　structure　characteristics,　the　PDI@MTi　shows　excellent　photocatalytic　activity　toward　the　disinfection　of　Staphylococcus　aureus　and　Cr(VI)　reduction,　with　1.0-　and　10.3-fold　enhancements,　respectively,　compared　with　unadorned　MTi.　The　synergic　effects　of　the　micro　polarisation　field,　multiple　active　sites,　and　a　C-N　bonded　interface　contributed　to　photoactivity　enhancement.　This　work　demonstrates　the　potential　of　using　MTi　as　a　platform　for　constructing　FLPs-containing　heterogeneous　photocatalysts　and　provides　new　strategies　to　control　carrier　separation.　©　2022　Elsevier　B.V.