A robust and efficient route to modify the chemical and physical properties of polycrystalline copper (Cu) wires via versatile plasma electrolysis is presented. Silica (SiO$_{2}$) nanoparticles (11 nm) are introduced during the electrolysis to tailor the surface structure of the Cu electrode. The influence of these SiO$_{2}$ nanoparticles on the structure of the Cu electrodes during plasma electrolysis over a wide array of applied voltages and processing time is investigated systematically. Homogeneously distributed 3D coral-like microstructures are observed by scanning electron microscopy on the Cu surface after the in-liquid plasma treatment. These 3D microstructures grow with increasing plasma processing time. Interestingly, the microstructured copper electrode is composed of CuO as a thin outer layer and a significant amount of inner Cu$_{2}$O. Furthermore, the oxide film thickness (between 1 and 70 µm), the surface morphology, and the chemical composition can be tuned by controlling the plasma parameters. Remarkably, the fabricated microstructures can be transformed to nanospheres assembled in coral-like microstructures by a simple electrochemical treatment.