Hierarchically　porous　materials　are　highly　valued　for　their　large　surface　areas　and　tunable　pore　architectures,　making　them　promising　heterogeneous　catalysts　for　photoinduced　electron　transfer-reversible　addition-fragmentation　chain　transfer　(PET-RAFT)　polymerization.　However,　the　specific　influence　of　pore　structure　on　catalytic　performance　remains　poorly　understood.　In　this　study,　hierarchically　porous　conjugated　organic　polymers　(COPs)　were　synthesized　using　a　silica　hard-template　method　and　employed　as　photocatalysts　for　PET-RAFT　polymerization.　Under　white　LED　light　irradiation,　the　effects　of　template　size　and　concentration　on　pore　structure　and　photocatalytic　performance　were　systematically　investigated.　Notably,　a　silica　template　with　a　concentration　of　60　mg/mL　and　a　particle　size　of　300　nm　produced　a　COP　with　an　average　pore　size　of　6.91　nm,　which　exhibited　the　best　photocatalytic　performance.　The　polymerization　rate　under　these　conditions　was　2.5　times　higher　than　that　of　the　control.　The　synergy　among　micropores,　mesopores,　and　macropores　enhanced　photocatalytic　efficiency　by　increasing　surface　area,　promoting　mass　transfer,　and　improving　charge　carrier　mobility.　Spectroscopic　and　electrochemical　analyses　further　revealed　that　the　optimized　pore　structure　significantly　enhances　charge　carrier　dynamics　by　facilitating　charge　separation　and　migration.　This　structural　modulation　effectively　reduces　charge　recombination,　thereby　improving　the　photocatalytic　efficiency　in　PET-RAFT　polymerization.　These　findings　provide　valuable　insights　into　the　rational　design　of　porous　photocatalysts　for　advanced　PET-RAFT　systems.　©　2025　Elsevier　Inc.