[4][3]: 219  Naples yellow was used in ancient Egypt and Mesopotamia, finding widespread application during the Hellenistic and Roman periods.

[3]: 221  Prior to its earliest occurrences in European paintings, the pigment was commonly employed in pottery, glazes, enamels, and glass.

A Latin treatise from the late 17th century by Andrea Pozzo referred to the pigment as luteolum napolitanum, which is the first recorded use of the term "Naples yellow"; its English name first appeared in print in 1738.

[6] It was not until the late eighteenth century that Naples yellow was generally recognized as a synthetic pigment of lead antimonate.

[6] The Italians first adopted Naples yellow as an enamel for tin-glazed pottery, or maiolica, from the beginning of the sixteenth century.

A piece of glass from the site of Amenhotep II's palace at Thebes (now at the Victoria and Albert Museum) is one of the earliest known examples.

[3]: 248  Naples yellow has frequently appeared on the palettes of European painters such as Anton Raphael Mengs, Francisco Goya, Jacques-Louis-David, Jean-Auguste-Dominique Ingres, Eugène Delacroix, and Paul Cézanne.