Maneuvering　spatial　photo-induced　charge　modulation/separation　over　semiconductor-based　photocatalysts　represents　an　enduring　challenge　in　solar-powered　photoredox　catalysis,　but　suffers　from　sluggish　charge　transport　kinetics,　confined　light　absorption　scope,　limited　active　species,　and　rapid　charge　recombination　rate.　Herein,　we　conceptually　demonstrate　the　elaborate　design　of　all　transition　metal　chalcogenides　(TMCs)-comprising　heterostructures　via　a　facile,　controllable,　and　precise　cascade　cation　exchange　strategy.　This　progressive　route　strategically　extends　the　light　absorption　of　TMCs,　engenders　elegant　heterostructured　interface,　and　furnishes　favorable　energy　level　alignment.　The　resultant　TMCs　heterostructures　demonstrate　markedly　enhanced　and　multifarious　photoactivities,　owing　predominantly　to　the　robust　interfacial　electronic　coupling　and　applicable　energy　level　configuration　among　the　building　blocks,　synergistically　resulting　in　the　reinforced　charge　transfer　impetus　and　considerably　prolonged　charge　lifespan.　Our　work　would　provide　an　emerging　avenue　to　fine　tuning　of　vectorial　charge　motion　via　such　a　judicious　interface　modulation　strategy　for　solar-to-chemical　energy　conversion.　©　2022　Elsevier　Inc.