The synthesis of a 3-fold symmetric cofacial organic cage (COC) through Cu(I)-catalyzed azide-alkyne cycloaddition is reported. The COC can function as an efficient receptor for carcinogenic polycyclic aromatic hydrocarbons to intercalate them in its intrinsic cavity through donor-acceptor and π···π stacking interactions. The association constants (Ka) are in the range of 3.7 × 10(4) to 1.3 × 10(6) M(-1). X-ray diffraction analysis authenticated that the polycyclic aromatic hydrocarbons (PAHs) are intercalated in the interior of the COC.