Electrowinning is the oldest industrial electrolytic process. The English chemist Humphry Davy obtained sodium metal in elemental form for the first time in 1807 by the electrolysis of molten sodium hydroxide.
Electrorefining of copper was first demonstrated experimentally by Maximilian, Duke of Leuchtenberg in 1847.
James Elkington patented the commercial process in 1865 and opened the first successful plant in Pembrey, Wales in 1870. The first commercial plant in the United States was the Balbach and Sons Refining and Smelting Company in Newark, New Jersey in 1883.