Painted designs are an early development, some remarkably fine work made before 3000 bce coming from excavations at Ur and elsewhere in Mesopotamia, as well as urns from Banshan in Gansu that date back to 2000 bce.

The earliest pottery colours appear to have been achieved by using slips stained with various metallic oxides (see above Slip decorating). At first these were undoubtedly oxides that occurred naturally in the clay; later they were added from other sources. Until the 19th century, when pottery colours began to be manufactured on an industrial scale, the oxides commonly used were those of tin, cobalt, copper, iron, manganese, and antimony. Tin oxide supplied a useful white, which was also used in making tin glaze (see above Decorative glazing) and occasionally for painting. Cobalt blue, ranging in colour from grayish blue to pure sapphire, was widely used in East Asia and Europe for blue-and-white porcelain wares. Cupric oxide gives a distinctive series of blues, cuprous oxide a series of greens, and, in the presence of an excess of carbon monoxide (which the Chinese achieved by throwing wet wood into the kiln), cupric oxide yields a bluish red. This particular colour is known as reduced copper, and the kiln is said to have a reducing atmosphere. (For the effect of this atmosphere on the colour of the biscuit body, see above Drying, turning, and firing).The colours obtained from ferric iron range from pale yellow to black, the most important being a slightly orange red, referred to as iron red. Ferrous iron yields a green that can be seen at its best on Chinese celadon wares. Manganese gives colours varying from the bright red purple similar to permanganate of potash to a dark purplish brown that can be almost black. The aubergine purple of the Chinese was derived from this oxide. Antimony provides an excellent yellow.

Pottery colours are used in two ways—under the glaze or over it. Overglaze painting is executed on a fired clay body covered with a fired glaze, underglaze painting, on a fired, unglazed body (which includes a body that has been coated with raw or unfired, glaze material).

Earthenware and stoneware are usually decorated with underglaze colours. After the body is manipulated into the desired shape it is fired. It is then painted, coated with glaze, and fired again. The second firing is at a lower temperature than the first, being just sufficient to fuse the glaze. In the case of most tin-glazed wares the fired object was first coated with the tin glaze, then painted, then fired again. The painting needed exceptional skill, since it was executed on the raw glaze and erasures were impossible. The addition of a transparent lead glaze over the painted decoration needed a third firing. In 18th-century Germany especially tin-glazed wares were decorated with colours applied over the fired glaze, as on porcelain. The wares were sometimes called Fayence-Porcellaine.

The body and glaze of most hard porcelain are fired in one operation, since the fusion temperature of body and glaze is roughly the same. Underglaze colours are limited because they must be fired at the same temperature as the body and glaze, which is so high that many colours would “fire away” and disappear. Although the Chinese made some use of copper red, underglaze painting on porcelain is more or less limited to cobalt blue, an extremely stable and reliable colour that yields satisfactory results under both high- and low-temperature firings. On soft porcelain, manganese was sometimes used under the glaze, but examples are rare. All other porcelain colours were painted over the fired glaze and fixed by a second firing that is much lower than the first.

Underglaze pigments are known as high-temperature colours, or colours of the grand feu. Similarly, overglaze colours are known as low-temperature colours, or colours of the petit feu. Other terms for overglaze colours are enamel colours and muffle colours, the latter name being derived from the type of kiln, known as a muffle kiln, in which they are fired. Overglaze colours consist of pigments mixed with glaze material suspended in a medium, such as gum arabic, with an alkaline flux added to lower the melting point below that of the glaze. They were first used in Persia on earthenware (minai painting) in the 12th century and perhaps at the same date on Chinese stoneware made at Cizhou.

Lustre decoration is carried out by applying a colloid suspension of finely powdered gold, silver, platinum, or copper to the glazed and fired object. On a further, gentle firing, gold yields a purplish colour, silver a pale straw colour, platinum retains its natural hue, and copper varies from lemonish yellow to gold and rich brown. Lustre painting was invented by early Islamic potters.

Pottery may be gilded or silvered. The earliest gilding was done with gold mixed with an oil base. The use of gold ground in honey may be seen on the finest porcelain from Sèvres during the 18th century, as well as on that from Chelsea. Toward the end of the same century, gold was applied as an amalgam, the mercury subsequently being volatilized by heating. Silver was used occasionally for the same purposes as gold but with time has nearly always turned black through oxidation.

Transfer printing

The transfer print made from a copper plate was first used in England in the 18th century. In the 20th century transfers from copper plates were in common use for commercial wares, as were lithographic and other processes, such as silkscreen printing, which consists of rubbing the colour through a patterned screen of textile material. Combinations of hand-painted and transfer decorations were often used. The outline or other part of the decoration was applied with a transfer print, then parts of the design, such as leaves, flowers, clothing, or water, were painted in.