The first known use of silver was in the Near East in Anatolia and Mesopotamia during the 4th and 3rd millennium BC, the Early Bronze Age. Archaeological findings of silver and lead objects together with litharge pieces and slag have been studied in a variety of sites. Although this has been interpreted as silver being extracted from lead ores, it has been also suggested that lead was added to collect silver from visible silver minerals embedded in host rock. In both cases silver would be retrieved from lead metal by cupellation.
During the following Iron Age, cupellation was done by fusing the base metals with a surplus of lead. The bullion or product of this fusion was then heated in a cupellation furnace to separate the noble metals.  Mines such as Rio Tinto, near Huelva in Spain, became an important political and economic site around the Mediterranean Sea, as well as Laurion in Greece.  Around 500 BC control over the Laurion mines gave Athens political advantage and power in the Mediterranean so that they were able to defeat the Persians.
During the Roman times, the empire needed large quantities of lead to support the Roman civilization over a great territory; they searched for open lead-silver mines in areas they conquered. Silver coinage became the normalised medium of exchange, hence silver production and mine control gave economic and political power. In Roman times it was worth mining lead ores if their content of silver was 0.01% or more.
The origin of the use of cupellation for analysis is not known. One of the earliest written references to cupels is Theophilus Divers Ars in the 12th century AD.  The process changed little until the 16th century. 
Small-scale cupellation may be considered the most important fire assay developed in history, and perhaps the origin of chemical analysis.  Most of the written evidence comes from the Renaissance in the 16th century. Vannoccio Biringuccio, Georg Agricola and Lazarus Ercker, among others, wrote about the art of mining and testing the ores, as well as detailed descriptions of cupellation. Their descriptions and assumptions have been identified in diverse archaeological findings through Medieval and Renaissance Europe. By these times the amount of fire assays increased considerably, mainly because of testing ores in the mines to identify the availability of its exploitation. A primary use of cupellation was related to minting activities, and it was also used in testing jewelry.  Since the Renaissance, cupellation became a standardised method of analysis that has changed little, demonstrating its efficiency. Its development touched the spheres of economy, politics, warfare and power in ancient times.