A series of thirteen new silver(I) double and multiple salts containing 4-nitrophenylethynide (L), namely AgL·4AgCF3COO·CH3CN (1), AgL·5AgCF3COO·3CH3CN (2), 3AgL·4AgCF3COO·2CH3CN (3), 3AgL·7AgCF3COO·6CH3CN (4), AgL·3AgC2F5COO·CH3CN (5), 4AgL·4AgC3F7COO·3CH3CN (6), 2AgL·4AgCF3COO·NC(CH2)2CN (7), AgL·3AgCF3COO·CH3CN·0.5NC(CH2)4CN (8), AgL·3AgC2F5COO·CH3CN·NC(CH2)4CN (9), 4AgL·12AgCF3COO·4(m-NCC6H4CN)·H2O (10), AgL·2[CF2(CF2COOAg)2]·4.5H2O (11), AgL·CF2(CF2COOAg)2·AgCF3COO·H2O (12) and AgL·CF2(CF2COOAg)2·AgC2F5COO·H2O (13), have been synthesized and characterized by X-ray crystallography. All these compounds contain the multinuclear silver–ethynide supramolecular synthon R–CC⊃Agn (R = 4-nitrophenyl; n = 3, 4, 5). High-dimensional metal–organic frameworks are achieved in these complexes via the linkage of characteristic carboxylate-bridged infinite silver chains by nitro–silver coordination or weak interactions. In addition, the nitrophenyl group exhibits its versatile ability to form other intermolecular interactions such as nitro⋯nitro, π⋯π, and C–H⋯O hydrogen bonding to stabilize the network structure. Furthermore, several factors affecting the supramolecular architectures, including the incorporation of nitriles and/or bidentate perfluorocarboxylates as co-existing ligands are also discussed.