Vinylene-linked　covalent　organic　frameworks　(COFs)　are　promising　photocatalysts　owing　to　their　fully　conjugated　skeletons　that　facilitate　charge　carrier　mobility.　Constructing　donor-acceptor　(D-A)　architectures　could　further　enhance　photoinduced　charge　generation　and　transport,　thus　promoting　photocatalysis.　Therefore,　three　D-A-type　vinylene-linked　COFs　were　fabricated　via　Knoevenagel　polymerization　for　efficient　photocatalysis.　By　varying　the　donor　moieties　from　phenyl　to　2,5-dimethylbenzene　and　3,3’-dimethyl-1,1’-biphenyl　in　the　skeletons,　the　light-harvesting,　optical-bandgap,　and　charge-transfer　properties　of　the　COFs　were　precisely　regulated.　All　three　COFs　exhibited　attractive　photocatalytic　hydrogen　evolution　rates　(HERs)　upon　visible-light　irradiation,　especially　that　fabricated　using　2,4,6-trimethyl-1,3,5-triazine　(TM)　and　3,3’-dimethyl[1,1’-biphenyl]-4,4’-dicarboxaldehyde　(DMA,　TM-DMA-COF).　TM-DMA-COF　exhibited　the　strongest　D-A　interactions,　excellent　charge-carrier　separation　and　transfer　kinetics,　and　a　reduced　energy　barrier　for　H2　formation.　Thus,　it　afforded　the　highest　HER　of　4300　µmol　h−1　gcat−1,　surpassing　those　of　most　state-of-the-art　COF　photocatalysts.　This　study　provides　a　simple　and　effective　protocol　for　modulating　the　photocatalytic　activities　of　COFs　at　the　molecular　level　and　an　interesting　insight　into　the　relationship　between　structural　design　and　photocatalytic　performance.　©　2023　Dalian　Institute　of　Chemical　Physics,　the　Chinese　Academy　of　Sciences