Photocatalytic　oxygen　reduction　reaction　(ORR)　for　H2O2　production　in　the　absence　of　sacrificing　agents　is　a　green　approach　and　of　great　significance,　where　the　design　of　photocatalysts　with　high　performance　is　the　central　task.　Herein,　a　spatial　specific　S-scheme　heterojunction　design　by　introducing　a　novel　semiconducting　pair　with　a　S-scheme　mechanism　in　a　purpose-designed　Janus　core–shell-structured　hollow　morphology　is　reported.　In　this　design,　TiO2　nanocrystals　are　grown　inside　the　inner　wall　of　resorcinol-formaldehyde　(RF)　resin　hollow　nanocakes　with　a　reverse　bumpy　ball　morphology　(TiO2@RF).　The　S-scheme　heterojunction　preserves　the　high　redox　ability　of　the　TiO2　and　RF　pair,　the　spatial　specific　Janus　design　enhances　the　charge　separation,　promotes　active　site　exposure,　and　reduces　the　H2O2　decomposition　to　a　large　extent.　The　TiO2@RF　photocatalyst　shows　a　high　H2O2　yield　of　66.6 mM g−1 h−1　and　solar-to-chemical　conversion　efficiency　of　1.11%,　superior　to　another　Janus　structure　(RF@TiO2)　with　the　same　heterojunction　but　a　reversed　Janus　spatial　arrangement,　and　most　reported　photocatalysts　under　similar　reaction　conditions.　The　work　has　paved　the　way　toward　the　design　of　next-generation　photocatalysts　for　green　synthesis　of　H2O2　production.　©　2023　Wiley-VCH　GmbH.