Synthesis of polyoxometalates (Cu3Mo2O9 nanopowders) was obtained by using solvothermal method and confirmed by X-ray diffraction pattern, with orthorhombic crystalline structure belonging to the space group Pna21(33). Further, the synthesized Cu3Mo2O9 nanopowders were analyzed by using Raman, infrared, and photoluminescence studies. X-ray photoelectron spectroscopy study explained the oxidation states of Mo-3d, Cu-2p, and O-1s in Cu3Mo2O9 nanopowders. Field emission scanning electron microscopy images clearly revealed the formation of nanostructure randomly oriented to form an interconnected rout, which emerged as a good candidate for storing more charges at the surface of Cu3Mo2O9 nanopowders. The electrochemical studies, such as cyclic voltammetry, electro impedance analysis, and galvanostatic charging–discharging studies, were used to analyze its electrochemical properties. To ensure the stability of Cu3Mo2O9 nanopowders, continuous charging and discharging studies were conducted for 1000 cycles at a current density of 5 A g−1 and it exhibited good stability over a large number of cyclic studies with capacity retention of 99.2% after the first 500 cycles.