A series of novel double salts of silver(I) were isolated by dissolving Ag2C2 in a concentrated aqueous solution of RFCO2Ag (R-F = CF3, C2F5) and AgBF4. Different ancillary solvento ligands such as H2O, CH3CN, and C2H5CN were found to affect the crystallization process that led to the assembly of various silver(I) ca.aes with embedded C-2(2-) ions. 2Ag(2)C(2). 12CF(3)CO(2)Ag . 5H(2)O (1) consists of two independent C-2@Ag-7 cages, each having the shape of a basket with a square base. Ag2C2. 6CF(3)CO(2)Ag . 3CH(3)CN (2) contains a zigzag chain of edge-sharing triangulated dodecahedra, and 4Ag(2)C(2). 23CF(3)CO(2)Ag . 7C(2)H(5)CN .2.5H(2)O (3) features an unusual double-walled silver column constructed from the fusion of four different kinds of irregular polyhedra. Ag2C2. 10C(2)F(5)CO(2)Ag .9.5H(2)O (4), Ag2C2. 9C(2)F(5)CO(2)Ag . 3CH(3)CN .H2O (5), and Ag2C2. 6C(2)F(5)CO(2)Ag . 2C(2)H(5)-CN (6) all contain an edge-sharing double cage with each single cage in the shape of a square antiprism, a capped square antiprism, and a triangulated dodecahedron, respectively.