The selective conversion of alkynes into bromotriazoles over a single-component catalyst is highly desirable but presents significant challenges. In this study, we developed a robust copper-bonded polyoxomolybdates-based framework [Cu2(Mo6O20)]·2H2O (CPF-1), and it integrates the catalytic ability of Cu(I) site with the multielectron-transfer ability of polyoxometalates. As a result, CPF-1 exhibits favorable bifunctional catalytic activity for click chemistry and achieves 99% yield in the conversion of corresponding products to bromotriazoles. To our knowledge, CPF-1 represents the first heterogeneous catalyst that significantly enhances cascade reaction with excellent efficiency and sustainable recyclability. Additionally, the possible cascade catalytic mechanisms of these two reactions are also proposed.