Eight members of the Ag/1,2,4-triazole/polyoxometalates (POMs) hybrid supramolecular family, namely, [Ag-4(dmtrz)(4)][Mo8O26] (dmtrz = 3,5-dimethyl-1,2,4-triazole, 1), [Ag-6(3atrz)(6)][PMo12O40](2)center dot H2O (3atrz = 3-amino-1,2,4-triazole, 2), [Ag-2(3atrz)(2)](2)[(HPMo10Mo2O40)-Mo-VI-O-V] (3), [Ag-2(dmtrz)(2)](2)[(HPMo10Mo2O40)-Mo-VI-O-V] (4), [Ag-2(trz)(2)](2)[Mo8O26] (trz = 1,2,4-triazole, 5), [Ag-2(3atrz)(2)][Ag-2(3atrz)(2)(Mo8O26)] (6), [Ag-4(4atrz)(2)Cl][Ag(Mo8O26)] (4atrz = 4-amino-1,2,4-triazole, 7), and [Ag-5(trz)(4)](2)[Ag-2(Mo8O26)]center dot 4H(2)O (8), were synthesized through hydrothermal reactions of 1,2,4-triazole or its derivatives with appropriate silver salts and molybdates. Crystal structure analysis reveals that the POM-dependent Ag-1,2,4-triazolate units in these hybrid compounds form a novel tetranuclear cluster (1), a unique double calix[3]arene-shaped hexamer (2), zigzag chains (5 and 6), helix chains (3, 4, and 8), and an interesting looped chain (7). A series of hydrogen bonding-based supramolecular assemblies varying among the 0-D + 0-D (1 and 2), 0-D + 1-D (3 and 4), 1-D + 1-D (5 and 7), and 1-D + 2-D (6) modes between the organomatic cations and POM anions were observed in these structures. Moreover, the inorganic chain [Ag(Mo8O26)](n)(3n-) in 7 constructed by the building block [Mo8O26](4-) linked only via single Ag+ ion is unprecedented. Compound 8 is the first high-dimensional framework constructed from the [Ag-2(Mo8O26)](n)(2n-) rod-shaped subunits. These hybrid supramolecular compounds present interesting photochemical properties. The spectroscopic experiments show that they not only are potential semiconductor materials but also have interesting photoluminescence phenomena, including O -> Mo [LMCT] and intraligand [pi - pi*] emissions generated by internal heavy metal effect.