Four new silver(l) double salts (L2H)(4)[Ag-10(C-2)(CF3CO2)(12)(L)(2)].5H(2)O (1), [Ag-8(C-2)(CF3CO2)(6)(L)(6)] (2), [(Ag2C2)(AgC2F5CO2)(6)(L)(3)(H2O)].H2O (3), and (L-H3O)(2)[Ag-11(C-2)(2)(C2F5CO2)(9)(H2O)(2)].H2O (4) incorporating the hitherto unexplored ligand 4-hydroxyquinoline (L) have been synthesized by the hydrothermal method. Compound 1 features an unprecedented bicapped square-anti prismatic Ag-10 silver cage with an embedded C-2(2-) moiety, whereas the discrete supermolecule 2 bears a rhombohedral Ag-8 core similar to that previously found in Ag2C2.6AgNO(3). Compound 3 contains a discrete supramolecular complex whose core is a (C2)(2)@Ag-16 double cage constructed from the edge-sharing of two monocapped square antiprisms, which is completely surrounded by 12 pentafluoropropionate, 6 4-hydroxyquinoline, and 2 aqua ligands. The layer structure in 4 is constructed from a sinuous anionic silver column composed of fused irregular monocapped trigonal antiprisms each encapsulating a C-2(2-) dianion, with L.H3O+ species serving as hydrogen-bond connectors to adjacent columns.