Photocatalytic　CO2　reduction　(PCR)　is　limited　by　unsatisfied　activity　and　selectivity.　The　integration　of　molecular　photocatalysts　with　semiconductors　can　solve　the　above　two　issues　simultaneously.　However,　most　of　the　organic-inorganic　heterojunctions　are　bulky-based　morphologies,　which　are　still　restricted　by　the　control　of　surface　areas　and　charge　transfer.　Herein,　a　tandem　dual　Z-scheme　heterostructure　was　synthesized　by　assembling　cobalt　porphyrin　([meso-tetra　(4-sulfonate　phenyl)　porphyrinato],　CoTPPS)　on　hollow-structured　TiO2@ZnIn2S4　(H-TiO2@ZIS).　The　optimized　H-TiO2@ZIS@CoTPPS　exhibits　superior　solar　fuel　evolution　of　158.15　μmolCO　g−1·h−1　via　the　PCR　process,　which　is　superior　to　most　reported　TiO2　and　ZIS-based　photocatalysts.　The　exceptional　photocatalytic　performance　is　ascribed　to　enhanced　light　absorption,　elevated　surface　areas,　directed　charge　separation,　and　improved　CO2　activation.　Specifically,　the　double　built-in　electric　field　(IEF)　and　the　Zn-O　bond　of　dual　Z-scheme　structures　facilitate　fast　charge　separation.　Detailed　charge　transfer　dynamics　of　H-TiO2@ZIS@CoTPPS　are　investigated　by　experimental　characterizations　and　density　functional　theory　(DFT)　calculations.　This　investigation　provides　atomistic　insight　into　unique　dual　Z-scheme　heterostructure　and　offers　a　new　paradigm　for　solar-driven　energy　conversion　©　2025　Elsevier　B.V.