Conjugated　microporous　polymers　(CMPs)　have　emerged　as　a　class　of　promising　organic　photocatalysts　due　to　their　tailorable　polymer　monomers,　tunable　molecular　orbitals,　diverse　synthesis　strategies,　etc.　However,　as　with　most　single　photocatalysts,　even　finely　designed　CMPs　are　still　subject　to　the　recombination　of　photogenerated　carriers,　making　it　difficult　to　perform　photocatalysis　effectively.　Herein,　two　types　of　CMPs　containing　pyrazine　and　benzothiadiazole　units　(labeled　as　PzTP　and　BTTP,　respectively)　are　purposely　designed　and　successfully　assembled　them　into　hierarchical　hollow　spheres　(PzTP@BTTP)　by　sequential　polymerization　on　sacrificial　templates.　It　is　demonstrated　that　these　two　CMPs　with　matched　orbital　energy　level　structures　effectively　form　a　Z-scheme　heterojunction　with　photoelectronic　properties　superior　to　those　of　a　single　CMP.　Particularly,　the　PzTP@BTTP　hollow　heterojunction　CMP　is　capable　of　generating　H2O2　as　high　as　8.19 mmol　g−1　h−1　in　pure　water　under　blue　light　irradiation,　and　even　20.49 mmol　g−1　h−1　using　benzyl　alcohol　as　a　hole　sacrificial　agent,　exhibiting　great　competitiveness　in　this　field.　This　work　suggests　that　it　is　feasible　to　construct　efficient　heterojunction　photocatalysts　by　rationally　combining　CMPs　with　different　energy　level　structures,　which　opens　up　new　avenues　for　expanding　the　research　of　CMP-involved　organic　semiconductors　in　the　photocatalysis　area.　©　2025　Wiley-VCH　GmbH.