We demonstrate a novel chemical-free water-based technique to synthesize various forms of cuprous oxide nanostructures at room temperature. The self-assemblies of these nanostructures are formed by the anodic oxidation of Cu in deionized (DI) water. Direct growth of these nanostructures on SiO2/Si (100) substrate has been successfully achieved by tuning the bias voltage and the growth duration. A variety of nanostructures from one-dimensional nanowires to different complex two- and three-dimensional structures are successfully grown by this method. We show that the morphological evolution in the self-assembly of the structures strongly depends on the spatial electric field distribution on the substrate. Furthermore, the electrical devices made from these nanowire networks exhibit promising photon sensing characteristics under white light illumination and can be exploited for future applications in photodetection and photovoltaic studies at the nanoscale level.