The design and assembly of polyoxometalate-resorcin[4]-arene-based metal-organic molecular materials are particularly attractive for their elegant structures and potential functions. By applying a newly designed resorcin[4]arene ligand (TPC4R-II), a copper(I)-coordinated polyoxometalate-based metal-organic molecular material, namely, [Cu-6(I)(Br)(3)(TPC4R-II)(3)(PMo12O40)]center dot 8H(2)O (1), was rationally assembled. Three copper(I)-coordinated resorcin[4]arenes are held together by a central [PMo12O40](3-) to yield a supramolecular propeller. 1 features efficient catalytic performances for oxidation desulfurization (ODS) and azide-alkyne cycloaddition (AAC) reactions. This work affords a feasible method for the nanosized polyoxometalate-based metal-resorcin[4]arene assemblies by well combinating two types of large composites as well as low coordination metal cations.