The key monomer TMBP was prepared via a facile one-step Yamamoto coupling in high yield . The Knoevenagel condensation between TMBP and benzaldehyde was performed in a mixture of benzoic acid and benzoic anhydride under 180 ℃, affording the model molecule 2,2',6,6'-tetrastyryl-4,4'-bipyridine in a yield of 85% (synthesis detailed in the Supporting Information). The structures of these new compounds were unambiguously characterized by NMR, MALDI-TOF MS and single crystal X-ray diffraction analyses. The packing diagram of the model molecule showed a -dimer arrangement of the neighbouring molecules with a distance of 3.43 Å, manifesting the distinct - interaction. By using the condition of the model reaction, TMBP was copolymerized with 1,4-diformylbenzene (DFB) or 4,4biphenyldialdehyde (BPDA), respectively, to synthesize COFs. In a typical protocol, TMBP, DFB, benzoic anhydride and benzoic acid in a molar ratio of 1:2:2:0.2 was sealed in glass ampoule and heated at 180 °C for 3 days (Scheme 1), leading to the generation of large amount of red-brown precipitates. After washed with base solution and organic solvents (methanol, THF and DCM), the resultant crude product was converted to yellow powder in 90 % isolated yield (termed COF-DFB). Similarly, another COF (COF-BPDA) were derived from a larger aldehyde monomer (BPDA) as yellow powders in 94 % yield.