A series of new silver(I)-containing MOFs [Ag-2(tr(2)ad)(2)](ClO4)(2) (1), [Ag-2(VO2F2)(2)(tr(2)ad)(2)]center dot H2O (2), [Ag-2(VO2F2)(2)(tr(2)eth)(2)(H2O)(2)] (3), and [Ag-2(VO2F2)(2)(tr(2)cy)(2)]center dot 4H(2)O (4) supported by 4-substituted bifunctional 1,2,4-triazole ligands (tr(2)ad = 1,3-bis(1,2,4-triazol-4-yl)adamantane, tr(2)eth = 1,2-bis(1,2,4-triazol-4-yl)ethane, tr(2)cy = trans-1,4-bis(1,2,4-triazol-4-yl)cyclohexane) were hydrothermally synthesized and structurally characterized. In these complexes, the triazole heterocycle as an N-1,N-2-bridge links either two adjacent Ag-Ag or Ag-V centers at short distances forming polynuclear clusters. The crystal structure of compound 1 is based on cationic {Ag-2(tr)(4)}(2+) fragments connected in a 2D rhombohedral grid network with (4,4) topology. The neighboring layers are tightly packed into a 3D array by means of argentophilic interactions (Ag center dot center dot center dot Ag 3.28 angstrom). Bridging between different metal atoms through the triazole groups assists formation of heterobimetallic Ag-I/V-V secondary building blocks in a linear V-Ag-Ag-V sequence that is observed in complexes 2-4. These unprecedented tetranuclear {Ag-2(VO2F2)(2)(tr)(4)} units (the intermetal Ag-Ag and Ag-V distances are 4.24-4.36 and 3.74-3.81 angstrom, respectively), in which vanadium(V) oxofluoride units possess distorted trigonal bipyramidal environment {VO2F2N}(-), are incorporated into ID ribbon (2) or 2D square nets (3, 4) using bitopic mu(4)-triazole ligands. The valence bond calculation for vanadium atoms shows +V oxidation state in the corresponding compounds. Thermal stability and photoluminescence properties were studied for all reported coordination polymers.