Alkoxy side-chain-flanked diarylsulfonamide serves as a reliable structural motif for constructing macrocyclic aromatic tetrasulfonamides. This 90°structural motif is persistent both in solution and in the solid state, which allows the one-step formation of tetrasulfonamide macrocycles. These macrocycles adopt a cone-shaped conformation in solution and in the solid state. For each molecule, an interior cavity surrounded by the aromatic residues is formed. The cavity sizes of the macrocycles can be tuned by incorporating aromatic residues of proper sizes. Guest (solvent) molecules are found in the cavities and bound by side chains. In solution, 1H NMR shows that the cone conformations undergo rapid interconversion at room temperature. The alkoxy side chains are found to be indispensable for maintaining the cone conformation. In addition, these porous molecules self-assemble into hollow tubular structures in the solid state. A variety of host molecules and building blocks for constructing nanoporous solid-state structures can be expected from these molecules.