Designing　photocatalysts　with　well-defined　structure-function　relationships　is　imperative　for　propelling　the　progression　of　desired　photocatalytic　oxidation.　Herein,　the　efficient　conversion　of　solar　energy　to　H2O2　and　subsequently　to　hydroxyl　radicals　(center　dot　OH)　is　achieved　through　a　synergistic　interplay　between　olefin　linkage　(-C　=　C-)　and　spatially　separated　benzene-triazine　dual　reaction　sites　within　covalent　organic　frameworks　(COFs).　The　upgraded　-C　=　C-　can　increase　the　conjugation　degree　of　COFs,　which　establishes　an　expanded　superstructure　for　boosting　charge　separation/transfer　and　stability.　This　precise　modulation　renders　more　opportunities　for　the　hot　electrons　to　migrate　to　the　benzene　site　for　solar-to-H2O2　generation,　and　to　the　triazine　site　for　H2O2-to-center　dot　OH,　separately.　The　optimized　center　dot　OH　generation　pathway　enables　remarkable　oxidation　performances　against　recalcitrant　organic　pollutants,　and　pathogenic　microorganisms　under　visible　light　irradiation.　This　work　provides　new　insights　for　tuning　the　synergistic　interactions　of　various　building　blocks　within　the　COFs　for　the　selective　generation　of　highly　reactive　center　dot　OH　for　environmental　remediation.