In conclusion, we have established an efficient synthetic strategy that can combine a D2h symmetrical building block 2,2',6,6'tetramethyl-4,4'-bipyridine with C2 symmetrical aromatic dialdehyde linkers to construct vinylene-linked COFs through Knoevenagel condensation in a mixed solvent of benzoic anhydride/benzoic acid. The possible reaction mechanism involves the self-catalyzed benzoylation of the used pyridine-based monomer, which subsequently promoted the Knoevenagel condensation at the pyridylmethyl carbon atoms of this monomer. The as-synthesized COFs were highly crystallized in orthorhombic lattices, releasing relatively large surface areas. The fully πconjugated structures give rise to abundant semiconducting properties of the COFs, allowing for efficiently visible lightcatalyzed hydrogen evolution from water reduction. This strategy paves a low-cost, environmentally friendly pathway to enlarge the regimes of vinylene-linked COFs with complex geometric and topological structures, as well as intriguing properties.