Various decomposition products of C–O ether bond cleavage have been trapped in supramolecular architectures as templates based on hydrothermal reaction of three-component metal–carboxylate–phen, which not only results in the formation of [5]pseudorotaxane structure, 3D porous framework and supramolecular structure, but also provides directly crystallographic evidence to explain how the C–O ether bond breaks during decomposition.