Reactions of AgX with 2,4,6-tri(2-pyridyl)-1,3,5-trazine (tpt) yielded three 3D highly symmetric isostructural coordination polymers (X = ClO4-, BF4-, and PF6-) and a dimer (X = CF3COO-), respectively. In the coordination polymers, anion-pi interactions are found between the multiatomic anions and tpt ligands. Systematic variation including synthetic methods, ratios of reactants, and solvents provides synthetic evidence proving that anion-pi interactions play a decisive role in assembly of the coordination polymers.