Polyoxometalate-based MOFs afford a great opportunity in terms of water oxidation. Herein, a new PMOF (SYNU-1) has been constructed with active CoMoO4 layers and TPPE ligands. In SYNU-1, each TPPE ligand bridges eight Co(II) and Mo(VI) cations to give a 3D (3,4,5)-connected (6(2).8(3).10)(6(3))(6(5).8(5)) framework. SYNU-1 CPE exhibits electroreduction toward nitrite and bromate. Furthermore, SYNU-1 catalyst demonstrates electrocatalytic OER activity with a low overpotential of 364 mV. Strikingly, the heterogeneous catalyst SYNU-1 shows a high O-2 yield (79.05%) for visible light water oxidation with good stability and reusability.