Functional modification of the covalent organic frameworks (COFs) has become an efficient strategy to expand its applications in various fields. In this investigation, an imine linked T−D COF has been synthesized via solvothermal method using 2,4,6‐tris(4‐aminophenyl)pyridine (TAPP) and 2,6‐dihydroxynaphthalene‐1,5‐dicarbaldehyde (DHNDA) as building blocks. While synthesizing T‐D COF, hydroxyl groups are strategically introduced to the adjacent sites of −C=N− bonds in the framework. Such a special structure enables a strong coordination between the loaded copper metal ion and the hydroxyl groups together with imine bounds in the COF layered structure. The obtained copper‐containing COF, (Cu@T−D COF) hybrid material was used as an efficient heterogeneous catalyst for the alkyne‐azide click chemistry reactions and showed excellent catalytic activity in methanol/water medium. Furthermore, this Cu@T−D COF is stable and easily recycled and reused without loss of its catalytic activity.

Cu(ii) and Pd(ii) ions were selectively coordinated within an imine-linked 2D COF that exhibited good catalytic performance towards a one-pot Suzuki coupling/oxidation cascade reaction.