The synthesis of several silver double helices containing bis(3,5dimethylpyrazolyl)-6-(R)-s-triazine ligands is described. The structure of two of them has been determined by X-ray difraction. Both derivatives represent the first reported examples of a new interaction mode for a triazine ring that involves a triazine N atom bridging two metal centers. Argentophilic contacts are also present. The Ag-N and Ag-Ag interactions have been demonstrated by theoretical studies, which also showed the clear influence of weak interactions with the counteranion and the effect of the symmetry of the triazine substituent. The different donor characters of these substituents allows a modulation of the strength of the bridging Ag-N-triazine interaction. Double pi-pi stacking, anion-pi interactions, hydrogen bonds, and hydrophobic effects are observed in an unusual highly symmetrical interpenetrated three-dimensional superstructure.