Six new silver(I) double salts, namely [Ag 13 (C 2 ) 2 (CF 3 CO 2 ) 9 (bipy) 4 (H 2 O) 3 ] (1), [Ag 18 (C 2 ) 2 (C 2 F 5 CO 2 ) 18 (bipyH) 4 ]·3H 2 O (2), [Ag 6 (C 2 )(CF 3 CO 2 ) 4 (bpp)] (3), [Ag 6 (C 2 )(C 2 F 5 CO 2 ) 5 (bppH)] n (4), [Ag 6 (C 2 )(CF 3 CO 2 ) 5 (bppH)] n (5) and [Ag 23 (C 2 ) 4 (CF 3 CO 2 ) 15 (bpp) 6 ]·H 2 O (6) (bipy=4,4′-bipyridine, bpp=bis(4-pyridyl)propane), have been hydrothermally synthesized and structurally characterized. In complex 1, the building units [Ag 24 (C 2 ) 4 (CF 3 CO 2 ) 16 (H 2 O) 6 ] are connected by bipy ligands to form a two-dimensional network, which are further linked into a three-dimensional architecture via argentophilic interactions. Complex 2 is composed of two independent [Ag(bipyH) 2 ] 3+ cations and a [Ag 16 (C 2 ) 2 (C 2 F 5 CO 2 ) 18 ] 6− cluster, whose core is a (C 2 ) 2 @Ag 16 double cage constructed from edge-sharing of two monocapped square antiprisms. Complex 3 has a two-dimensional architecture generated from bpp-bridged silver(I) columns. The virtually iso-structural complexes 4 and 5 each has a branched-tree architecture. The backbone is composed of fused silver(I) double cages, with C22- species embedded in its stem and an exterior coat comprising anionic perfluorocarboxyate and protonated bpp ligands. Complex 6 exhibits a two-dimensional architecture in which the basic building unit is an unusual silver(I) column composed of four consecutively fused C 2 @Ag n cages.