Typically, functionalization at nitrogen to generate pyridinium cations, makes pyridine ring favorable for electrophilic and/or nucleophilic substitution. Very recently, we reported a Knoevenagel condensation at the three methyl carbons in one pyridine promoted upon quaternization, leading to the formation of several pyridinium-cored vinylene-linked COFs with high crystallinities and quite large surface areas, suggesting an excellent efficiency in the activation of a multitopic monomer . N-acyl pyridinium has been found as a highly active intermediate formed in the process of pyridine-catalyzed hydrolysis of acid anhydride, or as one type of efficient acylation reagent from the treatment of pyridine with an acyl donor . With these reasons in our mind, our effort is to explore a much lower-cost, less-toxic and concise method to construct vinylene-linked COFs by virtue of methyl substituted pyridine-based monomer, and attempt to establish the optimized reaction conditions and corresponding thermodynamically controlled mechanism. In this work, we present the preparation of two vinylene-linked COFs with orthorhombic reticular topology by condensation of D2h-symmetric 2,2',6,6'-tetramethyl-4,4'-bipyridine (TMBP) as a tetratopic monomer with the ditopic linear aromatic dialdehydes in benzoic anhydride and benzoic acid. The reaction mechanism manifested that the pyridine units in monomer TMBP enable catalyzing their benzoylation via the cleavage of benzoic anhydride solvent molecules, thus helpfully activating the aryl α-carbon atoms for Knoevenagel reaction. The resulting COFs with high crystallinities and surface areas, were considerably characterized. Their -extended conjugated skeletons endow them with excellent semiconducting properties and corresponding application, such as, visible light catalysis of water-splitting hydrogen evolution.