A novel inorganic-organic hybrid, {Na[Tb(L)(H2O)4]3(SiW12O40)}·4H2O, in which L = 4-hydroxypyridine-2,6-dicarboxylic acid (chelidamic acid), was prepared and characterized by elemental analyses, Fourier transform infrared spectroscopy, and single-crystal X-ray diffraction. It consists of a trinuclear terbium cluster bonded to a Keggin-type polyoxotungstate. In the terbium cluster three crystallographically equivalent Tb3+ ions are bridged by carboxylate oxygen atoms belonging to three chelidamic acid units to form an equilateral triangle. These triangle units connect to each other through hydrogen-bonding and anion-π interactions. A CSD survey was carried out focusing on the cation and the ligand roles in the structure formation of this type of compounds. Finally, DFT calculations were used to analyse the role of the anion-π interactions that are important in the formation of 1D supramolecular assemblies in the solid state. The noncovalent interaction plot (NCIplot) computational tool has been used to characterize the anion-π interaction.