The earliest form of metallurgy was hammering copper. Native copper was first used by Old World Neolithic people beginning about the 8th millennium BC; and by New World in South American cultures beginning between 3600 and 1500 BC.
The next step, smelting (again of copper) appeared at Catal Hoyuk in Turkey, about 6000 BC; lead appears to have been added to the metal working about this same time. Mining of native materials began about 5000 BC. The earliest gold so far is from Varna in Bulgaria, about the same time. The earliest goldworking in the Americas to date is from the Jiskairumoko site of Peru, 3600 and 1500 BC.