 Solid-state 13C and 15N CP-MAS NMR data adequately reflected the presence of four nonequivalent PrDtc ligands in the tetranuclear lead(II) N,N-dipropyldithiocarbamate (PrDtc), [Pb4{S2CN(C3H7)2}8] (I); the spin–spin coupling constants 3J(15N–207Pb) for the ligands were estimated. It was shown by 13C MAS NMR that the chemisorption binding of AuCl3 from a solution in 2M HCl using lead(II) dipropyldithiocarbamate is accompanied by complete redistribution of the PrDtc ligands from Pb(II) to Au(III) coordination sphere; this gives the double complex of [Au{S2CN(C3H7)2}2][PbCl3] (II). Upon crystallization from an acetone–toluene mixture (3 : 1), this complex was isolated as the solvated form ([Au{S2CN(C3H7)2}2][PbCl3] ⋅ 1/2CH3C6H5)n (IIa), which was characterized by X-ray diffraction (CIF file CCDC no. 1978947). The cationic part of the complex is represented by non-centrosymmetric gold(III) complex ions, [Au{S2CN(C3H7)2}2]+, which are combined by pairs of nonequivalent Au···S secondary bonds, thus forming supramolecular pseudo-polymer chain ([Au{S2CN(C3H7)2}2]+)n. The 1D polymeric trichloroplumbate(II) anion, {[Pb(μ2-Cl)3]–}n, acts as the counter-ion. The C–H···Cl hydrogen bonds between the anionic and cationic chains lead to formation of channels in the crystal lattice, which are occupied by solvating toluene molecules.