Two remarkable polyoxometalate-bridged Cu(I)- and Ag(I)-thiacalix[4]arene dimers, namely, [Cu-4(SiW12O40)(L)(2)(DMF)(2)]center dot 2EtOH center dot DMF (1-Cu) and [Ag-4(PMo12O40)(L)(2)]center dot OH (1-Ag), were prepared by using a new thiacalix[4]arene, metal cation and polyoxometalate (L = tetra[2-(ethylthio)-1-methyl-1H-imidazole]-thiacalix[4]arene). In 1 -Cu and 1-Ag, two thiacalix[4]-arenes were linked together by one [SiW12O40](4-) or [PMo12O40](3-) anion via two metal cations to give a molecular dimer. Further, adjacent dimers were extended into a high-dimensional supramolecular architecture through hydrogen bonds. Markedly, these molecular dimers are exceedingly stable in organic solvents and then were employed as efficient catalysts for catalytic oxidation desulfurization as well as the azide-alkyne "click" reaction.