Two novel inorganic–organic hybrids constructed from Keggin-type polyanions and multinuclear copper clusters based on 1-H-1,2,3-benzotriazole (HBTA), [CuI8(BTA)4(HBTA)8(SiMo12O40)]·2H2O (1) and [CuII6(OH)4(BTA)4(SiW12O40)(H2O)6]·6H2O (2), have been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, elemental analyses, IR spectra and thermogravimetric (TG) analyses. In compound 1, eight CuI ions were linked by twelve HBTA/BTA ligands to form an octanuclear CuI cluster, which is connected by SiMo12O404− anion with two bridging O atoms and two terminal O atoms to construct a one-dimensional (1D) wave-like chain. The octanuclear copper unit represents the maximum subunit linked just by amine ligands in the POMs system. In 2, four BTA ligands linked five CuII ions constructing a pentanuclear “porphyrin-like” subunit, which is connected by another CuII ion to form a 1D metal–organic band. The SiW12O404−polyanions as tetradentate inorganic linkages extend the 1D band into a two-dimensional (2D) network with (83)2(85·10) topology. To the best of our knowledge, compounds 1 and 2 represent the first examples of inorganic–organic hybrids based on metal-HBTA multinuclear subunits and polyoxometalates. The photocatalysis and electrochemical properties have been investigated in this paper.