[(3,5-(CF₃)₂Pz)(AgL)₂]⁺[Ag₅(3,5-(CF₃)₂Pz)₆(CH₃CN)]⁻ (L = 2-(N,N-diethylanilino-4-yl)-4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine) shows bright and tunable emissions influenced by its supramolecular structure. Columnar stacks are assembled via cooperative interactions that include Ag^I⋯Ag^I argentophilic bonding, π⋯π stacking and Ag^I⋯π interactions.