The earliest recorded metal employed by humans appears to be gold, which can be found free or "native". Small amounts of natural gold have been found in Spanish caves dating to the late Paleolithic period, 40,000 BC. Silver, copper, tin and meteoric iron can also be found in native form, allowing a limited amount of metalworking in early cultures. Early metallurgy using native copper is documented at sites in Anatolia and at the site of Tell Maghzaliyah in Iraq, dating from the 7th/6th millennia BC. 
Certain metals, such as tin, lead, and copper can be recovered from their ores by simply heating the rocks in a fire or blast furnace in a process known as smelting. The first evidence of copper smelting, dating from the 6th millennium BC, has been found at archaeological sites in Majdanpek, Jarmovac and Pločnik, in present-day Serbia. The site of Pločnik has produced a smelted copper axe dating from 5,500 BC, belonging to the Vinča culture. The Balkans and adjacent Carpathian region were the location of major Chalcolithic cultures including Vinča, Varna, Karanovo, Gumelnița and Hamangia, which are often grouped together under the name of Old Europe. The Carpatho-Balkan region has been described as earliest metallurgical province in Eurasia, with a scale and technical quality of metal production in the 6th-5th millennia BC that totally overshadows that of any other contemporary production centre.
The earliest documented use of lead (possibly native or smelted), dating from the 6th millennium BC, is from the late Neolithic settlements of Yarim Tepe and Arpachiyah in Iraq. The artifacts suggest that lead smelting may have predated copper smelting.
Copper smelting is documented at sites in Anatolia and at the site of Tal-i Iblis in southeastern Iran from c. 5000 BC.  
Copper smelting is first documented in the Delta region of northern Egypt in c. 4000 BC, associated with the Maadi culture. This represents the earliest evidence for smelting in Africa.
The Varna Necropolis, Bulgaria, is a burial site located in the western industrial zone of Varna, approximately 4 km from the city centre, internationally considered one of the key archaeological sites in world prehistory. The oldest gold treasure in the world, dating from 4,600 BC to 4,200 BC, was discovered at the site. The gold piece dating from 4,500 BC, found in 2019 in Durankulak, near Varna is another important example.  Other signs of early metals are found from the third millennium BC in Palmela, Portugal, Los Millares, Spain, and Stonehenge, United Kingdom. The precise beginnings, however, have not be clearly ascertained and new discoveries are both continuous and ongoing.
In approximately 1900 BC, ancient iron smelting sites existed in Tamil Nadu.  
In the Near East, about 3,500 BC, it was discovered that by combining copper and tin, a superior metal could be made, an alloy called bronze. This represented a major technological shift known as the Bronze Age.
The extraction of iron from its ore into a workable metal is much more difficult than for copper or tin. The process appears to have been invented by the Hittites in about 1200 BC, beginning the Iron Age. The secret of extracting and working iron was a key factor in the success of the Philistines.
Historical developments in ferrous metallurgy can be found in a wide variety of past cultures and civilizations. This includes the ancient and medieval kingdoms and empires of the Middle East and Near East, ancient Iran, ancient Egypt, ancient Nubia, and Anatolia in present-day Turkey, Ancient Nok, Carthage, the Greeks and Romans of ancient Europe, medieval Europe, ancient and medieval China, ancient and medieval India, ancient and medieval Japan, amongst others. Many applications, practices, and devices associated or involved in metallurgy were established in ancient China, such as the innovation of the blast furnace, cast iron, hydraulic-powered trip hammers, and double acting piston bellows.
A 16th century book by Georg Agricola, De re metallica, describes the highly developed and complex processes of mining metal ores, metal extraction, and metallurgy of the time. Agricola has been described as the "father of metallurgy".