The dicopper-substituted gamma-Keggin silicotungstate TBA(4)[gamma-H2SiW10O36Cu2(mu-1,1-N-3)(2)] (I, TBA = tetra-n-butylammonium) could act as an efficient precatalyst for the regioselective 1,3-dipolar cycloaddition of organic azides to alkynes. Various combinations of substrates (four azides and eight alkynes) were efficiently converted to the corresponding 1,2,3-triazole derivatives in excellent yields without any additives. The present system was applicable to a larger-scale cycloaddition of benzyl azide to phenylacetylene under solvent-free conditions (100 mmol scale) in which 21.5 g of the analytically pure corresponding triazole could be isolated. In this case, the turnover frequency and the turnover number reached up to 14 800 h(-1) and 91 500, respectively, and these values were the highest among those reported for the copper-mediated systems so far. In addition, I could be applied to the one-pot synthesis of 1-benzyl-4-phenyl-1H-1,2,3-triazole from benzyl chloride, sodium azide, and phenylacetylene. The catalyst effect, kinetic, mechanistic, and computational studies show that the reduced dicopper core plays an important role in the present 1,3-dipolar cycloaddition.