Display omitted •The Ag(CN)2−3 trimer was found in Cu(Dach)2-Ag(CN)2-Cu(Dach)2Ag(CN)23 complex.•This entity is stabilized by unsupported argentophilic interaction.•MP2 interaction energy for this trimer is equal to −6.95 kcal/mol.•Energy decomposition revealed the prominent role of electrostatics and dispersion.•Normal vibrations of the Ag⋯Ag⋯Ag interaction confirmed its weak character. Crystal structure study of a copper(II) complex of cis-1,2-diaminocyclohexane (Dach), Cu(Dach)2-Ag(CN)2-Cu(Dach)2Ag(CN)23 (1) reveals the presence of unsupported Ag⋯Ag⋯Ag interactions with the interatomic Ag⋯Ag distance of 3.230 Å. Detailed HF, MP2 and BLYP-D3 theoretical investigations of Ag(CN)2−3 trimer, together with AIM, NCI and EDA analyses verified these interactions as noncovalent AgAg bonds with the magnitude of a weak hydrogen bond, mainly electrostatically and dispersively driven.