In summary, this work reports a transformative strategy that allows for the construction of elusive vinylene-linked 2D COFs. It achieves this by decoupling the reversible crystallization step from the irreversible bond-forming event, thus solving a classic materials design challenge. Moreover, functional units like BTT are integrated into such crystalline, conjugated vinylene-linked COFs creates a paradigm where high crystallinity and linkage stability directly enable optimal porosity and efficient electron transfer. Consequently, this work marks a significant step toward durable, highly ordered vinylene-linked COFs, with clear potential to serve as benchmark organic semiconductors in demanding applications. This detour strategy may well be extended to produce a variety of such materials with different topological architectures, opening the door to customized porous solids.