Five new silver(I) triple salts: (Ag 2 C 2 )(AgNO 3 ) 4 (AgL 1 ) 2 (L 1 H) 2 (1), (Ag 2 C 2 )(AgCF 3 CO 2 ) 2 (AgL 1 ) 2 (L 1 H) 1/2 (2), [(Ag 2 C 2 )(AgCF 3 CO 2 ) 4 (L 2 )(H 2 O)]·(L 2 H 2 ) (3), (Ag 2 C 2 )(AgNO 3 ) 3 (AgL 3 ) 2 (4), and [(Ag 2 C 2 )(AgCF 3 CO 2 ) 4 (AgL 3 ) 2 (H 2 O) 2 ]·H 2 O (5) (L 1 H=nicotinic acid, L 2 H=isonicotinic acid, L 3 H=2-pyrazinecarboxylic acid) have been synthesized by the hydrothermal method. All five compounds contain polyhedral silver(I) cages each encapsulating an acetylenediide dianion, C22-. In 1, C 2 @Ag 8 cages in the shape of bicapped trigonal prisms are interlinked by nitrate, L 1 , and L 1 H ligands into a three-dimensional architecture. In 2, silver(I) columns generated from fusion of triangulated dodecahedra are linked by L 1 into a layer structure. Compound 3 provides a rare example of a (L 2 H 2 ) + -pillared three-dimensional structure via hydrogen bonding. In 4, nitrate ligands together with L 3 link the C 2 @Ag 7 cages into a three-dimensional architecture. Compound 5 also exhibits a three-dimensional architecture generated from trifluoroacetate and L 3 -linked C 2 @Ag 8 cages.