Abstract Two 2D wavy hexagonal hexahydroxyl cyclotricatechylene (CTC) based COFs, CTC‐COF‐2 and CTC‐COF‐3 were synthesized through solvothermal reaction. The bowl‐shaped conformation caused CTC skeletons packed in a columnar manner with the same oriented units, thus forming an undulated structure. The gas adsorption properties of CTC‐COFs were investigated, which show the potential application abilities in hydrogen storage of CTC‐COFs. The introduction of pyrene into CTC‐COF‐3 makes it a potential semiconducting π‐conjugated material.