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Watercolor painting is extremely old, dating perhaps to the cave paintings of Paleolithic Europe, and has been used for manuscript illustration since at least Egyptian times but especially in the European Middle Ages. However, its continuous history as an art medium begins with the Renaissance. The German Northern Renaissance artist Albrecht Dürer (1471–1528), who painted several fine botanical, wildlife, and landscape watercolors, is generally considered among the earliest exponents of watercolor.

Botanical illustrations became popular during the Renaissance, both as hand-tinted woodblock illustrations in books or broadsheets and as tinted ink drawings on vellum or paper. Botanical artists have traditionally been some of the most exacting and accomplished watercolor painters, and even today, watercolors—with their unique ability to summarize, clarify, and idealize in full color—are used to illustrate scientific and museum publications.

During the 18th century, among the elite and aristocratic English classes, watercolor painting was one of the incidental adornments of a good education; mapmakers, military officers, and engineers used it for its usefulness in depicting properties, terrain, fortifications, field geology, and for illustrating public works or commissioned projects.

From the late 18th century through the 19th century, the market for printed books and domestic art contributed substantially to the growth of the watercolor medium. The three English artists credited with establishing watercolor as an independent, mature painting medium are Paul Sandby(1730–1809), often called the "father of the English watercolor"; Thomas Girtin (1775–1802), who pioneered its use for large format, romantic or picturesque landscape painting; and Joseph Mallord William Turner (1775–1851), who brought watercolor painting to the highest pitch of power and refinement, and created hundreds of superb historical, topographical, architectural, and mythological watercolor paintings.

The Elements of Drawing, a watercolor tutorial by English art critic John Ruskin, has been out of print only once since it was first published in 1857.

Watercolor painting also became popular in the United States during the 19th century; outstanding early practitioners included John James Audubon, as well as early Hudson River School painters such as William H. Bartlett and George Harvey.

Among the many 20th-century artists who produced important works in watercolor, Wassily Kandinsky, Emil Nolde, Paul Klee, Egon Schiele, and Raoul Dufy must be mentioned.

In America, the major exponents included Charles Burchfield, Edward Hopper, Georgia O'Keeffe, Charles Demuth, and John Marin (80% of his total work is watercolor).

The term "watercolor" refers to paints that use water-soluble, complex carbohydrates as a binder. Originally (in the 16th to 18th centuries), watercolor binders were sugars and/or hide glues, but since the 19th century, the preferred binder is natural gum arabic, with glycerin and/or honey as additives to improve plasticity and solubility of the binder, and with other chemicals added to improve product shelf life.

The traditional claim that "transparent" watercolors gain "luminosity" because they function like a pane of stained glass laid on paper—the color intensified because the light passes through the pigment, reflects from the paper, and passes a second time through the pigment on its way to the viewer—is false: watercolor paints typically do not form a cohesive paint layer, as do acrylic or oil paints, but simply scatter pigment particles randomly across the paper surface; the transparency consists in the paper being directly visible between the particles. Watercolors appear more vivid than acrylics or oils because the pigments are laid down in a more pure form with no or fewer fillers (such as kaolin) obscuring the pigment colors.