The　donor-acceptor-type　covalent　organic　frameworks　(COFs)　have　recently　gained　increasing　interest　in　photocatalysis,　but　the　photoinduced　electron-transfer　regimes　in　the　COFs　are　underexplored.　Herein,　we　demonstrate　a　designed　porphyrinic　COF　possessing　a　donor-acceptor　structure　together　with　its　photocatalytic　performance　in　aerobic　coupling　of　primary　amines.　The　COF　could　be　photoexcited　by　the　full　range　of　visible　light　to　generate　electron-hole　pairs　that　could　be　separated　by　donor-acceptor　pairs.　Electron　transfer　as　the　mechanism　of　the　reaction　from　anthracene　unit　to　porphyrin　unit　was　revealed　by　natural　transition　orbitals　analyses.　The　electrons　migrate　to　the　adsorbed　O2　to　generate　reactive　oxidative　species.　The　COF　displays　remarkable　photocatalytic　activities　in　the　coupling　of　amines　to　imines,　which　can　be　explained　mainly　by　the　sufficient　charge　separation　and　mobility,　benefiting　from　the　donor-acceptor　pairs　in　the　COF　and　their　interactions　to　the　reactants　and　intermediates.　©　2021　American　Chemical　Society.