Copper and copper oxide (Cu2O) nanoparticles (NPs) were synthesized by electrochemical route using 2.55 mM tri-sodium citrate (TSC) as a capping and reducing agent. Synthesis was conducted at 15 V and 373 K in the presence of pH 4.22 using a copper rod as a working electrode and a platinum wire as a reference electrode. The electrochemical set-up was kept in the air, as well as under inert nitrogen-purged conditions. Cu NPs were synthesized for the first time by the direct dissolution of Cu 2+ into the solution of the capping agent from the copper electrode in to the electrochemical cell. This means salt of copper was not used. NPs were characterized using UV–visible absorption spectroscopy, transmission electron microscopy (TEM), and X-ray diffraction (XRD) techniques. High-resolution TEM pictures showed the formation of a rod-shaped nanostructure. The lengths of copper rods were from 56.9 nm to 61.9 nm and the widths of nano-rods were, from 8.11 nm to 9.57 nm. Furthermore, the rod-shaped Cu2O NPs were tested for their catalytic applications in the electro-oxidation of methanol, where they showed excellent activity in terms of higher efficiency as well as kinetically low over-potential values.