Assembly of [Ag(CN)2]- units with diaminecopper(II) cation [Cu(pn)2]2+ (pn = 1,3-diaminopropane), gives the ionic complex [Cu(pn)2][Ag3(CN)5]. Single crystal X-ray analysis shows that this complex crystallizes in the triclinic, space group [image omitted], a = 7.675(3), b = 8.707(4), c = 8.807(4) Å, α = 66.624(7), β = 67.045(7), γ = 79.179(7)°, Z = 1. The whole complex has 3D architecture through metal-metal interactions and other weak interactions. The complex displays weak luminescence determined by argentophilicity at room temperature in the solid state.