In this work, under hydrothermal conditions, two novel polyoxometalates (POMs)-based CuII and CuI hybrid materials with 2,6-(1,2,4-triazole-4-yl)pyridine (L1), namely yellow block crystals [Cu2(L1)2(Mo4O13)] (1) and blue block crystals [Cu2(L1)3(H2O)2(Mo4O13)2] (2) have been designed and synthesized. These POM-based CuII and CuI hybrid materials 1–2 have been determined by single crystal X-ray diffraction analyses. In 1, these Mo8O26 4− anions and CuI centers are inter-linked by bidentate L1, which are arranged into the 1 D POMs-based CuI hybrid metal-organic framework. In 2, these L1 ligands bridge neighboring CuII centers and Mo8O26 4− anions, which ultimately form the unique 3 D POM-based CuII hybrid coordination framework of 2. Photocatalytic activities for decomposition of different organic dyes (Rhodamine B (RhB), methylene blue (MB) and methyl orange (MO)) have been investigated for 2, indicating that 2 are good candidates for the photocatalytic degradation of these organic dyes.