The ancient Egyptians applied enamels to stone objects, pottery, and sometimes jewellery, although to the last less often than in contemporaneous cultures in the Near East. The ancient Greeks, Celts, Georgians, and Chinese also used enamel on metal objects.

Enamel was also used to decorate glass vessels during the Roman period, and there is evidence of this as early as the late Republican and early Imperial periods in the Levant, Egypt, Britain and around the Black Sea. Enamel powder could be produced in two ways, either by powdering coloured glass, or by mixing colourless glass powder with pigments such as a metallic oxide.

Designs were either painted freehand or over the top of outline incisions, and the technique probably originated in metalworking. Once painted, enamelled glass vessels needed to be fired at a temperature high enough to melt the applied powder, but low enough that the vessel itself was not melted.

Production is thought to have come to a peak in the Claudian period and persisted for some three hundred years, though archaeological evidence for this technique is limited to some forty vessels or vessel fragments.

Ancient Persians used this method for colouring and ornamenting the surface of metals by fusing over it brilliant colours that are decorated in an intricate design and called it Meenakari. The French traveller, Jean Chardin, who toured Iran during the Safavidreign, made a reference to an enamel work of Isfahan, which comprised a pattern of birds and animals on a floral background in light blue, green, yellow and red. Gold has been used traditionally for Meenakari Jewellery as it holds the enamel better, lasts longer and its lustre brings out the colours of the enamels. Silver, a later introduction, is used for artifacts like boxes, bowls, spoons, and art pieces while copper which is used for handicraft products was introduced only after the Gold Control Act, which compelled the Meenakars to look for a material other than gold, was enforced in India. Initially, the work of Meenakari often went unnoticed as this art was traditionally used as a backing for the famous kundan or stone-studded jewellery. This also allowed the wearer to reverse the jewellery as also promised a special joy in the secret of the hidden design.

In European art history, enamel was at its most important in the Middle Ages, beginning with the Late Romans and then the Byzantine, who began to use cloisonné enamel in imitation of cloisonné inlays of precious stones. The Byzantine enamel style was widely adopted by the "barbarian" peoples of Migration Period northern Europe. The Byzantines then began to use cloisonné more freely to create images; this was also copied in Western Europe. The champlevé technique was considerably easier and very widely practiced in the Romanesque period. In Gothic art the finest work is in basse-taille and ronde-bosse techniques, but cheaper champlevé works continued to be produced in large numbers for a wider market.

From either Byzantium or the Islamic world, the cloisonné technique reached China in the 13–14th centuries. The first written reference to cloisonné is in a book from 1388, where it is called "Dashi ('Muslim') ware". No Chinese pieces that are clearly from the 14th century are known; the earliest datable pieces are from the reign of the Xuande Emperor (1425–35), which, since they show a full use of Chinese styles, suggest considerable experience in the technique.

Cloisonné remained very popular in China until the 19th century and is still produced today. The most elaborate and most highly valued Chinese pieces are from the early Ming Dynasty, especially the reigns of the Xuande Emperor and Jingtai Emperor (1450–57), although 19th century or modern pieces are far more common. Starting from the mid-19th century, the Japanese also produced large quantities of very high technical quality.

Grey clouds, typical enamel cooking gear from the Dutch DRU factory, popular in the 1950s

More recently, the bright, jewel-like colors have made enamel a favoured choice for jewellery designers, including the Art Nouveaujewellers, for designers of bibelots such as the eggs of Peter Carl Fabergé and the enameled copper boxes of the Battersea enamellers, and for artists such as George Stubbs and other painters of portrait miniatures.

A resurgence in enamel-based art took place near the end of the 20th century in the Soviet Union, led by artists like Alexei Maximovand Leonid Efros. In Australia, abstract artist Bernard Hesling brought the style into prominence with his variously sized steel plates.

Enamel was first applied commercially to sheet iron and steel in Austria and Germany in about 1850.Industrialization increased as the purity of raw materials increased and costs decreased. The wet application process started with the discovery of the use of clay to suspend frit in water. Developments that followed during the 20th century include enamelling-grade steel, cleaned-only surface preparation, automation, and ongoing improvements in efficiency, performance, and quality.