Thirteen new compounds based on different calix[4]arene derivatives, namely, [Mn(H3L1)2(phen)3] (1), [Cd(H3L1)2(phen)3] (2), [Ni(H3L1)2(phen)3] (3), [Co(H3.33L1)3(phen)3] (4), [Co(H3L1)2(en)3]·2H2O (5), [Zn2(H3L1)4(en)4(imi-4)]·H2O (6), [Zn6Na6(L2)4(OH)2(imi-4)(H2O)4]·5H2O (7), [Zn6Na6(L2)4(OH)2(tria-4)(H2O)4]·5H2O (8), [Co4Na2(L2)2(OH)2(H2O)6]·7H2O (9), [Cu3Na2(L2)2] (10), [Cu7Na4(L3)4(OH)2(H2O)5]·6H2O (11), [Zn2Na(L3)(OH)(H2O)]·2H2O (12) and [Pb4Na2(L3)2(OH)2] (13), where H4L1 = calix[4]arene, H4L2 = tetra(carboxymethoxy)calix[4]arene, H4L3 = tetra(carboxymethoxy)(p-tert-butyl)calix[4]arene, phen = 1,10-phenathroline, en = ethylenediamine, imi-4 = 1,4-bis(1H-imidazol-1-yl)butane and tria-4 = 1,4-bis(1,2,4-triazole-1-yl)butane, have been synthesized under hydrothermal conditions. Compounds 1 and 2 are isomorphous. In compound 1, the [Mn(phen)3]2+ unit acts as a guest and was trapped in the dimeric capsule of two H3L1 anions. The edge-to-face C–H⋯π interactions between the dimeric capsule hold the [Mn(phen)3]2+ unit and H3L1 anion together. Further, face-to-face π–π interactions link the capsules into a three-dimensional (3D) supramolecular architecture. Compounds 3, 4 and 6 show 0D discrete structures, which are further linked by C–H⋯π interactions to form 3D supramolecular architectures, respectively. In compound 5, the [Co(en)3]2+ cations and H3L1 anions are linked together through intermolecular hydrogen-bonding interactions, resulting in a 3D supramolecular architecture. Compound 8 is isomorphous with 7. In compound 7, Zn(II) and Na(I) ions are held together by L2 anions and imi-4 ligands to generate a 2D layer structure. Compounds 9 and 10 show chain structures, and the chains are linked through hydrogen bonds and C–H⋯π interactions to generate 3D supramolecular architectures, respectively. Compound 11 displays a column structure. Adjacent columns are linked by the C–H⋯O and O–H⋯O interactions to give a 2D supramolecular layer. Compound 12 exhibits a 1D ribbon-like structure. Compound 13 possesses a dimeric structure. The dimers are extended by the C–H⋯O interactions into a 1D supramolecular chain. The powder X-ray diffraction and luminescent properties have also been studied for the compounds.