The new silver(I) complexes (bpeH 2 ·2H 2 O)[Ag 8 (C 2 )(CF 3 CO 2 ) 8 (H 2 O) 2 ]·2H 2 O (1), [Ag 14 (C 2 ) 2 (C 2 F 5 CO 2 ) 10 (H 2 O) 4 (bpe)]·H 2 O (2), [Ag 7 (C 2 )(CF 3 CO 2 ) 2 (cba) 3 ] (3), [Ag 7 (C 2 )(C 2 F 5 CO 2 ) 5 (cbaH)(H 2 O) 2 ] (4) and (imH) 3 [Ag 8 (C 2 )(CF 3 CO 2 ) 9 ]·H 2 O (5) (bpe=trans-1,2-bis(4-pyridyl)ethylene, cbaH=4-cyanobenzoic acid, im=imidazole) contain polyhedral silver(I) cages each encapsulating a C22- dianion. Complex 1 provides the first example of a layer-type inclusion complex constructed with C 2 @Ag n polyhedra, whereas 2 and 3 both exhibit three-dimensional network structures, and 4 has a two-dimensional architecture. In 5, the imidazolium ions connect zig-zag anionic silver(I) columns to form a three-dimensional network via hydrogen bonding.