A copper-containing polyoxovanadate nanocluster, [(C2H5)4N]4 [V8Cu2O24]∙2H2O (1), was synthesized through reaction between the Cu(NO3)2∙3H2O and [(C2H5)4N]4VO3 in the molar ratio 1 : 4. Nanocluster 1 was characterized by IR, elemental analysis, XRD, SEM, TEM, and X-ray crystallography. The catalytic activity of 1 for the azide–alkyne cycloaddition of different terminal alkynes and organic azides generated in situ from sodium azide and different organic halides was tested. The protocol could afford the corresponding products in good to excellent yield at very low catalyst loadings (3.4 Mol%) under the optimized reaction conditions.
