A unique 3D framework containing three different types of nanoscale polyhedron cages was constructed by incorporating dinuclear [M-2(mu(2)-OH)-(COO)(4)] (M = Co, Ni) secondary building units and pyridyl-carboxylic-acid-supported tetracarboxylates. The assembled complexes possess isolated bifunctional single-site Lewis acid and Bronsted acid and can be used as highly efficient heterogeneous catalysts for the solvent-free Biginelli reaction with a high turnover frequency value of 338.4 h(-1). Interestingly, a variety of 3,4-dihydropyrimidin-2(1H)-ones have been obtained in high yields and short times.