A series of novel capsule-based coordination polymers (CPs), namely, [Cd(TTR4A)(L1)]·2.5H2O (1), [Cd(TTR4A)(L2)]·2DMF·2H2O (2), [Cd(TTR4A)(L3)]·2DMF·1.5H2O (3), [Cd(TTR4A)(L4)]·1.5H2O (4), and [Zn(TTR4A)(L1)]·DMF·H2O (5), have been synthesized via the reaction of a bowl-like tetrakis(1,2,4-triazol-ylmethylresorcin[4]arene (TTR4A) ligand with d10 metal salts in the presence of varied dicarboxylates (H2L1 = fumaric acid, H2L2 = 1,3-benzenedicarboxylic acid, H2L3 = 5-hydroxy-1,3-benzenedicarboxylic acid, H2L4 = biphenylethene-4,4′-dicarboxylic acid, and DMF = N,N-dimethylformamide). CPs 1–3 show rare two-dimensional (2D) capsule-based network structures. In 1–3, two TTR4A bowls share two Cd(II) cations to give a capsule, which is further extended by the dicarboxylates into 2D networks. CP 4 features a fascinating three-dimensional 3-connected framework structure constructed from bowl-like [Cd2TTR4A] units and L4 anions. In 5, each TTR4A coordinates with two Zn(II) cations by using two 1,2,4-triazole groups to generate a capsule, which is further connected by L1 ligands to afford a 2D network structure. Significantly, solid-state emissions and temperature variable luminescence were studied for 1–4. In particular, the remarkable metal-ion exchange property of CP 1 was investigated.