The double ionic-polymer complex ([Au(S 2 CNPr 2 ) 2 ][AgCl 2 ]) n (1) was prepared as an individual fixation form of gold(III) from NaCl solutions with silver(I) dipropyldithiocarbamate and was characterized by single-crystal X-ray diffraction and 13 C magic-angle spinning (MAS) NMR spectroscopy. The structure of 1 comprises two nonequivalent centrosymmetric complex cations [Au(S 2 CNPr 2 ) 2 ] + (A and B) and the discrete linear anion [AgCl 2 ] – . Gold(III) cations are linked by pairs of unsymmetrical secondary Au…S bonds to form linear supramolecular chains (…A…B…)n. Neighboring cations are additionally linked by [AgCl 2 ] – anions via secondary Ag…S and Cl…S bonds, the anions being involved in the overall stabilization of the supramolecular structure. The cation–anion interactions lead to a distortion of the linear configuration of the [AgCl 2 ] – anion. The character of thermolysis of 1 accompanied by quantitative regeneration of bound Au and Ag was established by simultaneous thermal analysis.