Polyoxometalate nanostructures have attracted much attention because of significant technical demands in applications such as catalysts, sensors, and smart windows. Therefore, researchers have recently developed many methods for the synthesis of these nanomaterials. However, these techniques have many visible flaws such as high temperatures or high pressure environments, various templates or additives, demanding and complicated synthesis procedures as well as the presence of impurities in the final products. We therefore propose a general strategy for the fabrication of particular polyoxometalate nanostructures by electrochemically assisted laser ablation in liquid (ECLAL). These polyoxometalates are usually simple as they typically contain two metals and are not soluble in water. This approach is a green, simple, and catalyst-free approach under an ambient environment. Apart from these merits, this novel technique allows researchers to choose and design interesting solid targets and to use an electrochemical approach toward the fabrication of polyoxometalate nanostructures for the purpose of fundamental research and for potential applications. Using the synthesis of Cu(3)Mo(2)O(9) nanorods as an example, we substantiate the validity of the proposed strategy. For the fabrication of Cu(3)Mo(2)O(9) nanostructures, we chose molybdenum as a solid target for laser ablation in liquid copper electrodes for the electrochemical reaction and water as a solvent for the ECLAL synthesis. We successfully fabricated Cu(3)(OH)(2)(MoO(4))(2) nanorods with magnetic properties. Interestingly, we obtained well-defined Cu(3)Mo(2)O(9) nanorods by annealing the Cu(3)(OH)(2)(MoO(4))(2) nanostructures at 500 °C. Additionally, the basic physics and chemistry involved in the ECLAL fabrication of nanostructures are discussed.